JP3273216B2 - 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 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 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, further improvement is required 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.

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.

On the other hand, there are many fields where a polymer having a narrow molecular weight distribution is required among the uses of polyolefin.
For example, in the case of an injection molding grade, it is necessary to narrow the molecular weight distribution in order to improve impact strength, and in the case of a film grade, in order to improve strength, transparency, anti-blocking properties, heat sealing properties, and the like.

The present inventors have previously found a novel catalyst component aiming at the above-mentioned product characteristics, and have already filed various patent applications (JP-A-3-64306, JP-A-3-153707, JP-A-3-185004, JP-A-3-252407 and JP-A-2-179485. When this catalyst component is used,
Although the molecular weight distribution became narrower and the product characteristics could be improved, further improvements are needed.

The present invention solves these problems by providing a polymer having a higher bulk density, a narrower particle size distribution, a significantly reduced amount of fine particles of polymer, a good flowability and a narrow molecular weight distribution. As a result of intensive studies aimed at obtaining the present invention, the present invention has been achieved.

[0007]

That is, the present invention provides [I] (1) a) a silicon oxide and / or an aluminum oxide, and b) a titanium compound or a compound obtained by reacting a titanium compound with a vanadium compound. (2) a) magnesium halide and b) a general formula Me (OR ¹ ) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from 1, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R ¹ is a hydrocarbon residue having 1 to 20 carbon atoms. And c) a titanium compound or a reaction product obtained by reacting a titanium compound with a reaction product obtained by reacting a vanadium compound with each other, and (3) a reaction product obtained by contacting an organoaluminum compound with the substance. And a solid catalyst component comprising: (II) a silicon compound having at least a Si—N—C bond and (III) an organometallic compound. This is a method for producing a polyolefin.

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 in that the molecular weight distribution is extremely narrow, the amount of hexane extracted is small, and the by-product of low polymer is very small. 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 includes: (I) (1) a) a silicon oxide and / or an aluminum oxide, (component [I]-(1) -a)) and b) a titanium compound or titanium. A reaction product obtained by reacting the compound with a vanadium compound (component [I]-(1) -b)); (2) a) magnesium halide (component [I]-(2) -b)) and B) The general formula Me (OR ¹ ) _n X _zn (where Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from 1, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R ¹ is a hydrocarbon residue having 1 to 20 carbon atoms. Reaction product obtained by mutually reacting a compound (component [I]-(2) -b)) and a titanium compound or a titanium compound and a vanadium compound (component [I]-(2) -c)) A solid catalyst component (component [I]) comprising: a reaction product obtained by further contacting (3) an organoaluminum compound (component [I]-(3)) with a material obtained by reacting the reaction product with a product; ) And [II] a silicon compound having at least one Si-NC bond, ([II] component) and [III] an organometallic compound ([III] component).

1. Solid catalyst component (component [I]) (1) Silicon oxide (component [I]) used in the present invention
-(1) -a)) means silica or silicon and the periodic table
It is a complex oxide with at least one other metal belonging to Groups 1 to 17 .

The aluminum oxide used in the present invention is alumina or aluminum and the periodic table 1 to 17
It is a mixed oxide of at least one other metal group. Representative oxides of silicon or aluminum and at least one other metal belonging to Group 1 to Group 17 of the periodic table include Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, and Al ₂ O
₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O
₃ · MgO · SiO ₂ , Al ₂ O ₃ · CuO, Al ₂ O
_{3 · Fe 2 O 3, Al} 2 O 3 · NiO, SiO 2 · Mg
Various natural or synthetic double oxides such as O 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.

Naturally, 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. it can.

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 (component [I]-(1) -b) to be brought into contact with the silicon oxide and / or the aluminum oxide are titanium or a halide or alkoxy halide of titanium and vanadium. Alkoxide, halogenated oxide and the like. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are preferable.
i (OR) _n X _4-n (where R represents 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). Those shown are preferred, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like, titanium tetrahalide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxytitanium, Ethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxymonochlorotitanium Titanium, tetrabutoxytitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium and the like can be mentioned.

As the trivalent titanium compound, a titanium tetrahalide such as titanium tetrachloride or titanium tetrabromide can be prepared by using hydrogen, aluminum, titanium, or any of the periodic tables 1 to 3 or 11
And titanium trihalide obtained by reduction with an organometallic compound of a Group 13 metal. The general formula Ti (O
R) _m X _4-m (where R represents an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and m is 0 <m ≦ 4). 4
And trivalent titanium compounds obtained by reducing a divalent 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 pentavalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxy vanadium, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. . Further, a combination of a titanium compound and a vanadium compound is often used. The V / Ti molar ratio at this time is 2/1 to 0.01 / 1.
Is preferable.

Component [I]-(1) -a) and component [I]-
The reaction ratio with (1) -b) is the same as that of component [I]-(1) -b).
The component [I]-(1) -a) per 1 g of the component [I]-
(1) -b) is used in an amount of 0.01 to 10.0 mmol, preferably 0.1 to 5.0 mmol, and more preferably 0.2 to 5.0 mmol.
It is desirable to use 2.0 mmol for the reaction.

Component [I]-(1) -a) and component [I]-
The reaction method with (1) -b) is not particularly limited as long as the object of the present invention is not impaired, but the reaction is carried out at a temperature of 20 to 20 in the presence of a sufficiently dehydrated inert hydrocarbon solvent (described later).
A method in which heating and mixing are performed at 300 ° C., preferably 50 to 150 ° C. for 5 minutes to 10 hours, or component [I]-(1)
It is preferable that the reaction product is obtained by directly contacting -i) with the component [I]-(1) -b) in the absence of an inert hydrocarbon.

After the component [I]-(1) -a) and the component [I]-(1) -b) are brought into contact with each other, they may be washed several times with an inert hydrocarbon. Component [I]-(1)
-B) After the component (I)-(1)-(b) is contact-reacted with the component (I), the inert hydrocarbon is removed by evaporation, and then the process proceeds to the step of contact reaction with the component (I)-(2). Is preferred. (2) As the magnesium halide (component [I]-(2) -a)) used in the present invention, a substantially anhydrous magnesium halide is used, and magnesium fluoride, magnesium chloride,
Examples thereof include magnesium bromide and magnesium iodide, and magnesium chloride is 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 phosphine.

The general formula Me (OR ¹ ) used in the present invention
a compound represented by _n X _zn (component [I]-(2)-
In b)) , the hydrocarbon residue of R ¹ is preferably an alkyl group, an aryl group, an aralkyl group, etc., and preferably has 1 to 8 carbon atoms. Examples of these compounds include NaOR ¹ , Mg (OR ¹ ) ₂ , Mg (OR ¹ ) X,
Ca (OR ¹ ) ₂ , Zn (OR ¹ ) ₂ , Cd (OR ¹ )
₂ , B (OR ¹ ) ₃ , Al (OR ¹ ) ₃ , Al (OR
¹ ) ₂ X, Al (OR ¹ ) X ₂ , Si (OR ¹ ) ₄ , S
i (OR ¹ ) ₃ X, Si (OR ¹ ) ₂ X ₂ , Si (OR
¹ ) Various compounds represented by X ₃ , Sn (OR ¹ ) _{4 and the} like can be mentioned. Preferred examples of these are Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₂ H ₅ ) C
1, Al (OCH ₃ ) ₃ , Al (OC ₂ H ₅ ) ₃ , Al
_{(On-C 3 H 7)} 3, Al (Oi-C 3 H 7) 3, A
_{l (On-C 4 H 9} ) 3, Al (Osec-C 4 H 9)
_{3, Al (Ot-C 4} H 9) 3, Al (OCH 3) 2 C
1, Al (OC ₂ H ₅ ) ₂ Cl, Al (OC ₂ H ₅ ) C
_{l 2, Al (Oi-C} 3 H 7) 2 Cl, Al (Oi-C
₃ H ₇ ) Cl ₂ , Al (OC ₆ H ₅ ) ₃ , Al (OC _{6
H 5) 2 Cl, Al (} OC 6 H 5) Cl 2, Al (OC
₆ H ₄ CH ₃ ) ₃ , Al (OC ₆ H ₄ CH ₃ ) ₂ Cl,
Al (OC ₆ H ₄ CH ₃ ) Cl ₂ , Al (OCH ₂ C _{6
H 5) 3, Si (OC} 2 H 5) 4, Si (OC 2 H 5) 3
Cl, Si (OC ₂ H ₅ ) ₂ Cl ₂ , Si (OC ₂ H ₅
) Cl ₃ , Si (OC ₆ H ₅ ) ₄ , Si (OC ₆ H
₅ ) ₃ Cl, Si (OC ₆ H ₅ ) ₂ Cl ₂ , Si (OC
_{6 H 5) Cl 3, Si} (OCH 2 C 6 H 5) may be mentioned compounds such as _4.

Magnesium halide (component [I]-
(2) -a)) and the general formula Me (OR ¹ ) _n X
The compound represented by the _z-n (component [I] - (2) - b))
As the titanium compound or the titanium compound and the vanadium compound (component [I]-(2) -c)) to be brought into contact with each other, specifically, various compounds used as the component [I]-(1) -b) are used. It is arbitrarily selected from a titanium compound and a vanadium compound, and has a component [I]-
The compound may be the same as or different from (1) -b), but is preferably a compound represented by the general formula Ti (OR) _n X
_4-n (where R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n satisfies 0 ≦ n ≦ 4). Desirably, tetraalkoxy titanium is particularly preferred.

Component [I]-(2) -a) and component [I]-
The reaction ratio with (2) -b) is determined by the component [I]-(2)-
B) / component [I]-(2) -a) (molar ratio) is 0.01
The range is preferably from 10 to 10, preferably from 0.1 to 5. The amount of component [I]-(2) -c) used is determined by the amount of component [I]-
(2) -c) / Component [I]-(2) -a) (molar ratio) is in the range of 0.01 to 5, preferably 0.05 to 1.0.

Component [I]-(2) -a), Component [I]-
The order of contact when (2) -b) and component [I]-(2) -c) are brought into contact with each other is not particularly limited,
Specifically, component [I]-(2) -a), component [I]-
(2) -b) and the component [I]-(2) -c) may be simultaneously contacted, or the components may be contacted and reacted in any order, but preferably the component [I]-
(2) -a), a method of simultaneously contacting the components [I]-(2) -b) and the components [I]-(2) -c), or a method of contacting the components [I]-(2) -a) and the components [I]-(2)-
B) was previously contacted as described above, and then the component [I]-
The method of contacting (2)-(c) is desirable. These contact reaction methods are not particularly limited, and include a ball mill, a vibration mill, a rod mill, and an impact mill at a temperature of 0 to 200 ° C. for 30 minutes to 50 hours in the presence or absence of an inert hydrocarbon solvent. A method of co-milling using an organic solvent such as an inert hydrocarbon, an alcohol, a phenol, an ether, a ketone, an ester, or a mixture thereof (these organic solvents may be used) Will be specifically described later).
A method of mixing and reacting at a temperature of 50 ° C., preferably 50 to 300 ° C. for 5 minutes to 10 hours, and then removing the solvent by evaporation may be used. In the present invention, component [I]-(2)-
After co-milling component b) and component [I]-(2) -b), the co-ground product is reacted with component [I]-(2) -c) in an organic solvent, and then the solvent is evaporated. The removal method is preferably used. I (3) The organoaluminum compound (component [I]-(3)) to be brought into contact with the reaction product of component [I]-(1) and component [I]-(2) is represented by the general formula: AlR _n X _{3 -N} (where R is a hydrocarbon group such as an alkyl group, an aryl group, or an aralkyl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, X is a halogen, and n is 0 <n ≦
3) are preferable, and specifically, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisopropylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, trimethylaluminum,
Examples thereof include triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tridecylaluminum, ethylaluminum sesquichloride, and the like. Of these, diethyl aluminum chloride and ethyl aluminum sesquichloride are particularly preferred. (4) The solid catalyst component used in the present invention is obtained by first reacting the components [I]-(1) and [I]-(2),
Thereafter, it is obtained by reacting component [I]-(3).

The reaction ratio of the components [I]-(1) and [I]-(2) is such that 0 g of the component [I]-(2) -a) per 1 g of the component [I]-(1) -a). 0.01 to 20 mmol, preferably 0.1 to 10 mmol, more preferably 0.2 to 20 mmol.
Desirably, it is set to 4.0 mmol. Component [I]-
Reaction product of (1) and [I]-(2) and component [I]-(3)
The reaction rate of component [I]-(3) / {component [I]-
(1) -b) + component [I]-(2) -c)｝ (molar ratio)
Is desirably 0.1 to 100, preferably 0.2 to 10, and more preferably 0.5 to 5.

The reaction method of the components [I]-(1) and [I]-(2) is not particularly limited, but the temperature is 0 to 200 ° C.
For 30 minutes to 50 hours, or a solvent inactive to a Ziegler catalyst, such as a hydrocarbon solvent, alcohols, phenols, ethers, ketones, esters, or a mixture thereof. In an organic solvent consisting of, 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, after treatment in an organic solvent, the organic solvent is removed. The removal method is desirable.

The method of contacting the reaction product of the components [I]-(1) and (I)-(2) with the component [I]-(3) is not particularly limited, but may be carried out in the presence of an inert hydrocarbon solvent. , Temperature 0
To 300 ° C, preferably 20 to 150 ° C for 5 minutes to 10
It is preferable to use a method of mixing and heating for a period of time and then removing the solvent. Of course, component [I]-(1),
The reaction operation for preparing the component [I]-(2) and the solid catalyst component should be performed in an inert gas atmosphere, and moisture should be avoided as much as possible.

The components [I]-(1), [I]-(2) 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, Examples thereof include decane, benzene, toluene, xylene, and the like, and mixtures thereof.

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 having 1 to 20 carbon atoms)
A hydrocarbon group such as an aralkyl group or an organic residue containing elements such as oxygen, nitrogen, sulfur and chlorine), specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol ,
Examples include heptanol, 2-ethyl-hexanol, octanol, phenol, chlorophenol, benzyl alcohol, methyl cellosolve, ethyl cellosolve and the like, and mixtures thereof.

The ethers to be used include those 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. Good), specifically, dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxaneanisole and the like. These may be used as a mixture.

The ketones to be used include compounds of the general formula R--CO--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. Good), specifically, 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 include those having 1 to 1 carbon atoms.
30 organic acid esters, specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate Isopropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate Phenyl salicylate, cyclohexyl p-oxybenzoate, salicyl sampendyl, ethyl α-resorcinate, methyl anisate,
Ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate, ethyl o-toluate,
ethyl m-toluate, methyl p-aminobenzoate, p
-Ethyl aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, ethyl naphthoate and the like. These may be used as a mixture.

The nitriles include, for example, acetonitrile, propionitrile, butyronitrile, pentyronitrile, benzonitrile, hexanonitrile and the like, and may be used as a mixture thereof. The amines include methylamine, ethylamine,
Examples thereof include diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine, and these may be used as a mixture. Thus, the components [I]-(1) and [I]-(2) are contact-reacted, and then the component [I]
-(3) is contact-reacted to obtain a solid catalyst component.

2. Silicon Compound (Component [II]) The silicon compound having at least one Si—N—C bond used in the present invention includes a compound represented by the general formula R ⁵ _a R ⁶ _b R ⁷ _c Si (NR ⁸ ) _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 and the like, a, b, c and d represent 0
≦ a <4, 0 ≦ b <4, 0 ≦ c <4, 0 <d ≦ 4, provided that 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 4} , HSi ｛N (CH ₃ ) _{2 ３ 3} ,
HSi ｛N (C ₂ H ₅ ) ₂ ｝ ₃ , CH ₃ Si ｛N (CH
₃ ) ₂ ｝ ₃ , CH ₃ Si ｛N (C ₂ H ₅ ) ₂ ｝ ₃ , C
₂ H ₅ Si ｛N (CH ₃ ) _{2 ３ 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 SiＣＨN (CH 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 ,

Si {NH (CH ₃ )} ₄ , S
i {NH (C ₂ H ₅ )} ₄ , HSi {NH (CH ₃ )}
₃ , HSi {NH (C ₂ H ₅ )} ₃ , CH ₃ S
i ｛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 ｛N
H (CH 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 (CH 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 , HC
H ₃ Si ｛N (CH ₃ ) ₂ ｝ ₂ , HC ₂ H ₅ Si ｛N
(CH ₃ ) ₂ ｝ ₂ , (CH ₃ ) ₂ Si ｛N (C
H ₃ ) ₂ ｝ ₂ , (CH ₃ ) (C ₂ H ₅ ) Si ｛N (CH
₃ ) ₂ ｝ ₂ , (CH ₃ ) (C ₂ H ₄ ) Si ｛N (C
H 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 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 ),

[0042] _{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

[0044]

Embedded image

[0045]

Embedded image

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

In the present invention, the amount of the silicon compound (component [II]) used is (component [II] / (component [I]-(1) -b) in component [I]) + component [I ]
-(2) -c) It is desirable that｝ (molar ratio) be 0.01 to 100, preferably 0.1 to 10, and more preferably 0.5 to 5.

3. Organometallic Compound (Component (III)) The catalyst used in the present invention comprises the solid catalyst component, the silicon compound, and an organometallic compound. The organometallic compound is known as one component of the Ziegler catalyst. Although organic metal compounds of Groups I to IV of the periodic table can be used, organic aluminum compounds and organic zinc compounds are particularly preferred. Specific examples include the general formulas R ₃ Al and R ₂ Al
X, RAlX ₂ , R ₂ AlOR, RAl (OR) X and an organoaluminum compound of R ₃ Al ₂ X ₃ (where R
Is an alkyl or aryl group having 1 to 20 carbon atoms, X is a halogen atom, R may be the same or different, or R ₂ Zn (where R is 1 to 20 carbon atoms)
And the two may be the same or different), and are represented by the following organic zinc compounds: trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tris
Examples include ec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumchloride, diisopropylaluminumchloride, ethylaluminumsexchloride, diethylzinc and a mixture thereof.

In the present invention, the amount of the organometallic compound (component (III)) used is not particularly limited.
Component [III] / {Component [I]-in component [I]-]
(1) -b) + component [I]-(2) -c)｝ (molar ratio)
Can be used in an amount of 0.1 to 1000, preferably 1 to 500. In the present invention, the solid catalyst component (component [I]) and the silicon compound (component [I]
The method of supplying the component (I)) and the organometallic compound (component (III)) to the polymerization reactor is not particularly limited, but the components (I), (II) and (III)
Desirable is a method of separately supplying the components, or a method of separately supplying the mixture of the component [II] and the component [III] and the component [I].

In the present invention, the organometallic compound component can be preferably used as a mixture or an addition compound of the organometallic compound and an organic acid ester. At this time, when the organic metal compound and the organic acid ester are used as a mixture, the organic acid ester is used in an amount of usually 0.1 to 1 mol, preferably 0.2 to 0.5 mol, per 1 mol of the organic metal compound. . 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, isopropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, Cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate,
p-cyclohexyl p-oxybenzoate, salicyl sampendyl, 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-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate,
Benzyl benzoate, methyl naphthoate, ethyl naphthoate and the like can be mentioned. Of these, benzoic acid, o- or p-tolylic acid or p-
-Alkyl esters of anisic acid, and methyl esters and ethyl esters thereof are particularly preferred.

4. Olefin Polymerization Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization.
In particular, the catalyst of the present invention can be suitably used for gas-phase polymerization, and the polymerization reaction is carried out in the same manner as an 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 preferred are 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 such as propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1 and ethylene having 3 to 12 carbon atoms It is suitably used for copolymerization of α-olefin, copolymerization of propylene with 1-butene, and copolymerization of ethylene with two or more other α-olefins.

Further, 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. In addition, the comonomer content at the time of copolymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, in the ethylene / α-olefin copolymer, Is preferably 0 to 40 mol%, more preferably 0 to 30 mol%.

[0055]

(Polymer property measurement method)

Melting point: Using a scanning calorimeter (DSC, manufactured by Seiko Denshi Co., Ltd.), melting once at 180 ° C. with a sample weight of 5 mg, cooling to −40 ° C., and then heating at a rate of 10 ° C./min. Was determined as the melting point. n value: using a Shimadzu flow tester (CFT-500), applying various loads 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.

[0056]

(Equation 1)

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. 400m inner volume containing 25 stainless steel balls with 1/2 inch diameter
1 g of stainless steel pot, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum.
Was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol.
, and the entire amount of the solution was added to the above three-necked flask and reacted under ethanol reflux for 3 hours. After cooling, the supernatant liquid was removed by decantation,
Drying under reduced pressure was performed for hours. Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and reacted under hexane reflux for 1 hour. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component. The amount of titanium in 1 g of the obtained solid catalyst component was 28 mg.
Met.

(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, bis (dimethylamino) dimethylsilane 0.2 mmol / hr and triethylaluminum at a rate of 50 mmol / hr, and the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.35.
Further, each gas is supplied while adjusting hydrogen to 15% of the total pressure, and the gas in the system is circulated by a blower while maintaining the total pressure at 8 kg / cm ² G, thereby intermittently extracting the produced polymer. While the polymerization was continued for 10 hours. 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 stirrer, and the long-term stable operation was excellent. The catalyst efficiency is 29
The activity was as high as 000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 0.98 g / 10 min and a density of 0.9203.
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 830 μm. Further, the melting point of this copolymer was 121.3 ° C., and the n value was 1.42, and the molecular weight distribution was extremely narrow.

Example 2 In conducting gas phase polymerization using the solid catalyst component prepared in Example 1, the bis (dimethylamino)
Gas phase polymerization was carried out in the same manner as in Example 1 except that bis (dimethylamino) methylsilane was used at 1.0 mmol / hr instead of dimethylsilane.
Even after the continuous operation for 48 hours, no polymer adhered to the inner wall and the agitator at all, and it was excellent in long-term stable operation. The catalyst efficiency is 270,000g copolymer / gTi
High activity, MFR 0.91 g / 10 min, density 0.
9210g / cm ^3, bulk density 0.46 g / cm ^3, a round particulate matter having the shape of an average particle diameter of 790μm was obtained. The melting point of this copolymer is 121.5 ° C., and the n value is 1.4.
3 and a very narrow molecular weight distribution.

Example 3 In conducting gas phase polymerization using the solid catalyst component prepared in Example 1, the bis (dimethylamino)
Gas-phase polymerization was performed in the same manner as in Example 1 except that bis (diethylamino) dimethylsilane 0.2 mmol / hr was used instead of dimethylsilane.
Even after the continuous operation for 48 hours, no polymer adhered to the inner wall and the agitator at all, and it was excellent in long-term stable operation. The catalyst efficiency is 280,000g copolymer / gTi
High activity, MFR 0.84 g / 10 min, density 0.
A round granular material having a shape of 9215 g / cm ³ , a bulk specific gravity of 0.45 g / cm ³ and an average particle size of 790 μm was obtained. The melting point of this copolymer was 122.0 ° C., and the n value was 1.4.
4 and the molecular weight distribution was very narrow.

Example 4 In conducting gas phase polymerization using the solid catalyst component prepared in Example 1, the bis (dimethylamino)
Gas phase polymerization was carried out in the same manner as in Example 1 except that bis (diethylamino) methylsilane was used at 1.0 mmol / hr instead of dimethylsilane.
Even after the continuous operation for 48 hours, no polymer adhered to the inner wall and the agitator at all, and it was excellent in long-term stable operation. The catalyst efficiency is 230,000g copolymer / gTi
High activity, MFR 0.96 g / 10 min, density 0.
9215g / cm ^3, bulk density 0.47 g / cm ^3, a round particulate matter having the shape of an average particle diameter of 730μm was obtained. The melting point of this copolymer was 122.0 ° C., and the n value was 1.4.
4 and the molecular weight distribution was very narrow.

Example 5 (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 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. 400m inner volume containing 25 stainless steel balls with 1/2 inch diameter
1 stainless steel pot, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum.
Was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol.
, and the entire amount of the solution was added to the above three-necked flask and reacted under ethanol reflux for 3 hours. After cooling, the supernatant liquid was removed by decantation,
Drying under reduced pressure was performed for hours. Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and reacted under hexane reflux for 1 hour. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component. The amount of titanium in 1 g of the obtained solid catalyst component was 30 mg.
Met.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r, bis (dimethylamino) dimethylsilane 0.2 mm
ol / hr and 50 mol of triethyl aluminum
1 / hr, while supplying each gas while adjusting the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.38 and hydrogen to 15% of the total pressure. While maintaining the total pressure at 8 kg / cm ² G, the gas in the system was circulated by a blower, and continuous polymerization was carried out for 10 hours while intermittently extracting the produced polymer. After completion of the polymerization, the inside of the autoclave was inspected. As a result, no polymer was adhered to the inner wall and the stirrer.
The catalyst efficiency was as high as 230,000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 0.98 g / 10 min, a density of 0.9214 g / cm ³ and a bulk density of 0.46 g.
/ Cm ³ and an average particle diameter of 800 μm. Further, the melting point of this copolymer was 121.9 ° C., the n value was 1.44, and the molecular weight distribution was extremely narrow.

Example 6 (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. 400m inner volume containing 25 stainless steel balls with 1/2 inch diameter
1 g of stainless steel pot, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum.
Was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol.
1 and 5 ml of 2-ethyl-hexanol, and the whole amount of the solution was added to the above three-necked flask and reacted for 3 hours under ethanol reflux. 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 reacted for 1 hour under hexane reflux. Thereafter, hexane was removed by blowing nitrogen at 70 ° C. to obtain a solid catalyst component. The amount of titanium in 1 g of the obtained solid catalyst component was 26 mg.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the solid catalyst component was added to an autoclave adjusted to 80 ° C.
r, bis (dimethylamino) dimethylsilane 0.2 mm
ol / hr and 50 mol of triethyl aluminum
1 / hr, while supplying each gas while adjusting the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.38 and hydrogen to 15% of the total pressure. While maintaining the total pressure at 8 kg / cm ² G, the gas in the system was circulated by a blower, and 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 240,000 g copolymer / gTi, which was extremely high. The produced ethylene copolymer had a melt flow rate (MFR) of 0.94 g / 10 min, a density of 0.9207 g / cm ³ and a bulk density of 0.45 g.
/ Cm ³ and an average particle diameter of 800 μm. The melting point of this copolymer was 122.3 ° C., and the n value was 1.45, and the molecular weight distribution was extremely narrow.

Example 7 In preparing the solid catalyst component in Example 1, the procedure of Example 1 was repeated except that 3.6 g of triethoxyboron was used instead of 4.2 g of triethoxyaluminum of Example 1. A solid catalyst component was prepared in the same manner, and gas phase polymerization was performed under the same conditions as in Example 1. Catalyst efficiency is 2
High activity of 10,000g copolymer / gTi, MFR
1.04g / 10min, density 0.9213g / c
m ³ , bulk specific gravity 0.44 g / cm ³ , average particle size 710 μm
Round granules of m shape were obtained. Further, the melting point of this copolymer was 122.3 ° C., and the n value was 1.46, and the molecular weight distribution was extremely narrow.

Example 8 The preparation of the solid catalyst component in Example 1 was repeated except that 2.9 g of diethoxymagnesium was used instead of 4.2 g of triethoxyaluminum of Example 1. Prepare a solid catalyst component in a similar manner,
Gas phase polymerization was performed under the same conditions as in Example 1. The catalyst efficiency is as high as 220,000g copolymer / gTi, and MFR
1.03 g / 10 min, density 0.9208 g / c
m ³ , bulk specific gravity 0.44 g / cm ³ , average particle size 720 μm
Round granules of m shape were obtained. Further, the melting point of this copolymer was 122.3 ° C. and the n value was 1.45, and the molecular weight distribution was extremely narrow.

Example 9 In preparing the solid catalyst component in Example 1, the procedure of Example 1 was repeated except that 3.1 g of tetraethoxysilane was used instead of 4.2 g of triethoxyaluminum of Example 1. A solid catalyst component was prepared in the same manner, and gas phase polymerization was performed under the same conditions as in Example 5. Catalyst efficiency is 1
High activity of 90,000g copolymer / gTi, MFR
0.81 g / 10 min, density 0.9224 g / c
m ³ , bulk specific gravity 0.45 g / cm ³ , average particle size 670 μm
Round granules of m shape were obtained. Further, the melting point of this copolymer was 121.5 ° C., the n value was 1.44, and the molecular weight distribution was extremely narrow. In preparing the solid catalyst component in Example 1, except that propionitrile was used instead of ethanol, a solid catalyst component was prepared in the same manner as in Example 1, and the same conditions as in Example 5 were used. For gas phase polymerization. The catalyst efficiency is as high as 200,000 g copolymer / g Ti, and the MFR is 0.91 g / 10 mi.
n, density 0.9215 g / cm ³ , bulk specific gravity 0.44 g
/ Cm ³ , an average particle size of 680 μm was obtained. The melting point of this copolymer is 122.0 ° C.
The value was 1.45 and the molecular weight distribution was extremely narrow.

Example 10 A solid catalyst component was prepared in the same manner as in Example 1 except that alumina was used instead of silica.
The gas phase polymerization was performed under the same conditions as described above. The catalyst efficiency is 170,
000g copolymer / gTi and high activity, MFR 0.75
A round granular material having a shape of g / 10 min, a density of 0.9228 g / cm ³ , a bulk specific gravity of 0.43 g / cm ³ , and an average particle size of 590 μm was obtained. The melting point of this copolymer is 12
At 2.4 ° C., the n value was 1.45 and the molecular weight distribution was extremely narrow.

Example 11 In the preparation of the solid catalyst component in Example 1, a solid catalyst component was prepared in the same manner as in Example 1 except that silica alumina was used instead of silica. Gas phase polymerization was performed under the same conditions as in Example 1. Catalyst efficiency is 1
High activity of 80,000g copolymer / gTi, MFR
0.89 g / 10 min, density 0.9222 g / c
m ³ , bulk specific gravity 0.43 g / cm ³ , average particle size 600 μm
Round granules of m shape were obtained. Further, the melting point of this copolymer was 122.4 ° C., and the n value was 1.45, and the molecular weight distribution was extremely narrow.

Example 12 In preparing the solid catalyst component in Example 1, 2.2 m of titanium tetrachloride was used instead of 2.2 ml of titanium tetrachloride.
A solid catalyst component was prepared in the same manner as in Example 1 except that 1 and 0.5 ml of triethoxyvanadyl were used, and gas phase polymerization was performed under the same conditions as in Example 1. The catalyst efficiency is as high as 220,000 g copolymer / gTi, the MFR is 0.84 g / 10 min, and the density is 0.9209.
g / cm ^3, bulk density 0.45 g / cm ^3, average particle size 6
Round granules of 70 μm shape were obtained. Further, the melting point of this copolymer was 122.2 ° C., and the n value was 1.45, and the molecular weight distribution was extremely narrow.

Example 13 In performing gas phase polymerization using the solid catalyst component prepared in Example 1, bis (dimethylamino) dimethylsilane and triethyl aluminum were
(Mole ratio) 0.04, and reacted at 60 ° C for 3 hours.
The polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out at a rate of mol / hr. The catalyst efficiency is 250,0
High activity with 00g copolymer / gTi, MFR 1.16g
/ 10min, a density 0.9215g / cm ^3, bulk density 0.46 g / cm ^3, a round particulate matter having the shape of an average particle diameter of 770μm was obtained. The melting point of this copolymer is 12
At 2.1 ° C, the n value was 1.45, and the molecular weight distribution was extremely narrow.

Example 14 (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. 400m inner volume containing 25 stainless steel balls with 1/2 inch diameter
1 g of stainless steel pot, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum.
Was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol.
, and the entire amount of the solution was added to the above three-necked flask and reacted under ethanol reflux for 3 hours. 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 under hexane reflux for 1 hour. Then 70 ° C
The hexane was removed by nitrogen blow to obtain a solid catalyst component. The amount of titanium in 1 g of the obtained solid catalyst component was 28 mg.
Met.

(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. In the autoclave, hot water flows into a jacket. The temperature was adjusted accordingly. 80
The above solid catalyst component was added to an autoclave adjusted to 25 ° C.
0 mg / hr, bis (dimethylamino) dimethylsilane 0.2 mmol / hr and triethylaluminum were supplied at a rate of 50 mmol / hr, and the butene-1 / ethylene molar ratio in the autoclave gas phase was 0.35.
Further, each gas is supplied while adjusting hydrogen to 15% of the total pressure, and the gas in the system is circulated by a blower while maintaining the total pressure at 8 kg / cm ² G, thereby intermittently extracting the produced polymer. While the polymerization was continued for 10 hours. 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 stirrer, and the long-term stable operation was excellent. The catalyst efficiency is 29
The activity was as high as 000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 0.98 g / 10 min and a density of 0.9203.
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 830 μm. Further, the melting point of this copolymer was 121.3 ° C., and the n value was 1.42, and the molecular weight distribution was extremely narrow.

Example 15 In conducting gas phase polymerization using the solid catalyst component prepared in Example 1, the bis (dimethylamino)
Gas phase polymerization was carried out in the same manner as in Example 1 except that bis (dimethylamino) methylsilane was used at 1.0 mmol / hr instead of dimethylsilane.
Even after the continuous operation for 48 hours, no polymer adhered to the inner wall and the agitator at all, and the stable long-term operation was excellent. The catalyst efficiency is 270,000 g copolymer / gT
i, high activity, MFR 0.91 g / 10 min, density 0.9210 g / cm ³ , bulk specific gravity 0.46 g / c
A round granular material having a shape of m ³ and an average particle size of 790 μm was obtained. Further, the melting point of this copolymer was 121.5 ° C. and the n value was 1.43, and the molecular weight distribution was extremely narrow.

Comparative Example 1 (a) Production of Solid Catalyst Component A 500-ml three-necked flask equipped with a stirrer and a reflux condenser was 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. 400m inner volume containing 25 stainless steel balls with 1/2 inch diameter
1 g of stainless steel pot, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of triethoxyaluminum.
Was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. 7.5 g of the reaction product and 5.0 g of tetrabutoxytitanium were added to 160 ml of dehydrated ethanol.
1 and the whole amount of the solution was added to the above three-necked flask, and reacted under ethanol reflux for 3 hours. After cooling, the supernatant liquid was removed by decantation,
Drying under reduced pressure was performed for hours. Next, 150 ml of hexane and 80 mmol of diethylaluminum chloride were added, and reacted under hexane reflux for 1 hour. Thereafter, hexane was removed by nitrogen blowing at 70 ° C. to obtain a solid catalyst component. The amount of titanium in 1 g of the obtained solid catalyst component was 28 mg.
Met.

(B) Gas phase polymerization The above solid catalyst component was added in an amount of 250 mg / h to an autoclave adjusted to 80 ° C. using the same gas phase polymerization apparatus as in Example 1.
r and triethylaluminum at 50 mmol / hr
At the rate of butene in the autoclave gas phase.
Each gas was supplied while adjusting the 1 / ethylene molar ratio to 0.27 and hydrogen to 17% of the total pressure,
While maintaining the total pressure at 8 kg / cm ² G, the gas in the system was circulated by a blower, and continuous polymerization was carried out for 10 hours while intermittently extracting the produced polymer. The catalyst efficiency is 20
0000g copolymer / gTi, MFR1.00g / 1
0 min, a granular material having 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 melting point of this copolymer was 122.5 ° C., the n value was 1.51, and the molecular weight distribution was wider than that of the examples of the present invention.

[0078]

The homopolymer or copolymer of the olefin using the solid catalyst component of the present invention, an organometallic compound and a silicon compound having at least one Si--N--C bond as a catalyst is particularly useful for the reaction during polymerization. There is little adhesion of the polymer to the vessel wall, and long-term stable operation is possible. Further, a polymer having a small decrease in polymerization activity and a narrow molecular weight distribution can be obtained. Particularly when applied to a film, it can exhibit many effects such as high strength, excellent transparency, and excellent antiblocking properties and heat sealing properties.

[Brief description of the drawings]

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

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────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-62016 (JP, A) JP-A-6-322016 (JP, A) JP-A 7-10929 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/65-4/658

Claims (1)

(57) [Claims] 1. (I) (1) a) a silicon oxide and / or
Or aluminum oxide; and b) a titanium compound or a reaction product obtained by reacting a titanium compound with a vanadium compound; and (2) a) a magnesium halide and b) a general formula Me (OR ¹ ) _n X _zn (here And Me is Na, Mg, Ca, Zn, Cd, B, A
an element selected from 1, Si and Sn , z is the valence of the element Me, n is 0 <n ≦ z, X is a halogen atom, and R ¹ is a hydrocarbon residue having 1 to 20 carbon atoms. And c) a titanium compound or a substance obtained by reacting a titanium compound and a reaction product obtained by reacting a vanadium compound with each other, and (3) a reaction product obtained by contacting an organoaluminum compound with the substance. And a solid catalyst component comprising: (II) a silicon compound having at least one Si—N—C bond; and (III) an organometallic compound. A method for producing a polyolefin.