JP3038667B2 - 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 relates to a method for producing a polyolefin having a low molecular weight component and a narrow molecular weight distribution. In addition, the polymer yield per solid and polymer yield per transition metal is significantly increased, thereby eliminating the need for steps to remove catalyst residues in the polymer, and reducing the finely powdered portion of the resulting polymer to reduce the average particle size. The present invention relates to a method for producing a polyolefin having a large particle size and good particle properties.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in this type of technical field, magnesium halide,
Many highly active catalysts are known in which an inorganic magnesium solid such as magnesium oxide or magnesium hydroxide is used as a carrier and a compound of a transition metal such as titanium or vanadium is supported on the carrier. However, in these known techniques, the molecular weight distribution of the obtained polyolefin is relatively wide, which causes, for example, a deterioration in blocking properties and heat sealing properties when applied to the film field. In order to produce a polyolefin having a low molecular weight component and a narrow molecular weight distribution, a method of adding an electron donor compound or treating the electron donor compound has been proposed, but the activity often decreases, and bulkiness is increased. Since the specific gravity is generally small, the average particle size is relatively small, and the particle size distribution is generally wide, there are many fine particles, and improvement in productivity and polymer handling has been strongly desired. Furthermore, the pelletization process, which has been increasing in recent years, has been omitted,
Improvements are still needed in order to use the powder polymer as it is on the processing machine. The present inventors have previously found a novel catalyst component in which the above-mentioned disadvantages have been improved, and have already filed various patent applications (JP-A-3-64306, JP-A-3-153).
707, JP-A-3-185004, JP-A-3-2524
07 etc.). When this catalyst component is used, a polymer having a relatively narrow molecular weight distribution and a high bulk density and a large average particle size can be obtained, but further improvement is required to further improve the quality in the field of film. . The present invention has been accomplished as a result of intensive studies with the aim of improving these drawbacks and obtaining a polymer having a low molecular weight component and a narrow molecular weight distribution with extremely high activity.

[0003]

That is, the present invention provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as catalysts, wherein the solid catalyst component comprises [I] at least a magnesium source represented by the general formula MgX
₂ (where X represents a halogen atom)
Titanium, solid material (solid component) containing magnesium and a halogen as essential components (a (I) component) [II] Formula AlR _n X _3-n (second (II)
Component) (where R is a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, and n is 0 <n <3), and [III] a general formula AlR _m (OR ') _n X _{3- (m + n)}
(Component [III]) (where R and R ′ are hydrocarbon groups having 1 to 24 carbon atoms, which may be the same or different, X represents a halogen atom, and m represents 0 ≦ m. <3, n is 0 <n ≦ 3, 0 <m
+ N ≦ 3). The present invention relates to a method for producing a polyolefin, comprising a substance obtained by mutually reacting alkoxyaluminum compounds represented by (+ n ≦ 3).

By using the method of the present invention, it is possible to produce a polyolefin having a very narrow molecular weight distribution, a small amount of hexane extracted, and a very small amount of by-products of a low polymer, with very high activity. 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.

<1> Solid catalyst component Component (I) The solid component used in the component (I) of the present invention is titanium,
It contains magnesium and halogen as essential components. (1) The titanium compound is not particularly limited, but has a general formula: Ti (OR) _m X _4-m (where R represents a hydrocarbon residue having 1 to 20 carbon atoms, X represents a halogen atom, and m represents 0 ≦ m ≦ 4), specifically, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxytitanium, and the like. Methoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, monoethoxytrifluorotitanium, monoethoxytribromotitanium, diethoxydifluorotitanium, diethoxydichlorotitanium, diethoxydibromotitanium, triethoxyfluorotitanium, triethoxychlorotitanium, Tetraethoxytitanium, monopropoxytrichlorotitanium, monoi Propoxytrichlorotitanium, dipropoxydichlorotitanium, diisopropoxydichlorotitanium, diisopropoxydibromotitanium, triisopropoxyfluorotitanium, tripropoxychlorotitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, monoiso Butoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxyfluorotitanium, tributoxychlorotitanium, triisobutoxychlorotitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetrasec-butoxytitanium, tetratert-butoxytitanium, monopen Toxitrichlorotitanium, dipentoxydichlorotitanium, tripentoxydimonochlorotitanium, tetra-n-pentyloxytitanium, tetracyclo Emissions chill oxytitanium, mono octyloxy trichloro titanium, di-octyloxy-dichloro titanium, tri-octyloxy monochloro titanium, tetra n
-Hexyloxytitanium, tetracyclohexyloxytitanium, tetra-n-heptyloxytitanium, tetra-
n-octyloxytitanium, tetra-n-ethylhexyloxytitanium, mono-2-ethylhexyloxytrichlorotitanium, di-2-ethylhexyloxydichlorotitanium, tri2-ethylhexyloxymonochlorotitanium,
Tetra-nonyloxytitanium, tetradecyloxytitanium, tetraisobornyloxytitanium, tetraoleyloxytitanium, tetraallyloxytitanium, tetrabenzyloxytitanium, tetrabenzhydryloxytitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, Triphenoxychlorotitanium, tri-o-
Xyleneoxychlorotitanium, tetraphenoxytitanium, tetra-o-methylphenoxytitanium, tetra-m
-Methylphenoxytitanium, tetra-1-naphthyloxytitanium, tetra-2-naphthyloxytitanium, or an arbitrary mixture thereof;
Titanium tetrachloride, monoethoxytrichlorotitanium, diethoxydichlorotitanium, monobutoxytrichlorotitanium,
Dibutoxydichlorotitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-n-hexyloxytitanium, tetra-n-
Octyloxytitanium, tetra-2-ethylhexyloxytitanium and the like are desirable.

(2) The magnesium compound is represented by the general formula MgX ₂ (where R represents a hydrocarbon residue having 1 to 20 carbon atoms;
Compounds represented by shown to) a halogen atom is mentioned,
Magnesium fluoride specifically, magnesium chloride, magnesium bromide, it is possible to increase the iodide magnesium, in particular MgCl ₂ is preferred. In the present invention,
These magnesium compounds are alcohols, esters,
It may be treated with an electron donor such as ketone, carboxylic acid, ether, amine and phosphine.

(3) In addition to the titanium compound and the magnesium compound, a general formula Me (OR) _p X _z-p (where Me is an element belonging to Groups I to IV of the periodic table, and z is an element M
The valence of e, p is 0 <p ≦ z, and 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. May be used. For example, NaOR, Mg (OR) ₂ , Mg
(OR) X, Ca (OR) ₂ , Zn (OR) ₂ , Cd
(OR) ₂ , B (OR) ₃ , Al (OR) ₃ , Al (O
R) ₂ X, Al (OR) X ₂ , Si (OR) ₄ , Si
(OR) ₃ X, Si (OR) ₂ X ₂ , Si (OR)
Various compounds represented by 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 (Osec-C ₄ H ₉ ) ₃ , Al
_{(Ot-C 4 H 9)} 3, Al (OCH 3) 2 Cl, Al
(OC ₂ H ₅ ) ₂ Cl, Al (OC ₂ H ₅ ) Cl ₂ , A
_{l (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 C
_{H 3) 3, Al (OC} 6 H 4 CH 3) 2 Cl, Al (O
C ₆ H ₄ CH ₃ ) Cl ₂ , Al (OCH ₂ C
_{6 H 3) 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 )
₄ , and the like.

(4) A method in which a silicon oxide and / or an aluminum oxide is further added to the titanium compound and the magnesium compound to cause mutual reaction can be used. The silicon oxide used in the present invention is a double oxide of silica or silicon and at least one other metal of Groups I to VIII 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 I to VIII of the periodic table. Representative oxides of silicon or aluminum and at least one other metal of Group I-VIII of the periodic table include Al ₂ O ₃ .MgO,
Al ₂ O ₃ .CaO, Al ₂ O ₃ .SiO ₂ , Al ₂ O
₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ ,
Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂
Various natural or synthetic double oxides such as O ₃ .NiO and SiO ₂ .MgO can be exemplified. Here, the above formula is not a molecular formula but a structure only, 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.
Desirably, the silica has a pore size of 200 μm, a pore volume of 0.3 ml / g or more, and a surface area of 50 m ² / g or more. In use, it is desirable to perform a baking treatment in advance at 200 to 800 ° C. by an ordinary method.

(5) Organic compounds such as alcohols, phenols, ethers, ketones, esters, amines, nitriles and the like are further added to the above titanium compound and magnesium compound (including in the presence thereof), and You may make it react. Among them, alcohols are particularly preferable, and such alcohols are represented by the general formula ROH (R is
To 20, preferably 1 to 12 hydrocarbon groups such as an alkyl group, an aryl group, and an aralkyl group). Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-, butanol, 3- Methyl-1-butanol, 2
-Methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-
1-pentanol, 4-methyl-2-pentanol, 2
-Ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol,
2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2,2,4
-Trimethyl-1-pentanol, 1-nonanol, 5
Nonano-3,5-dimethyl-4-heptanol, 2,
6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, 2,6,8-trimethyl-4-nonanol, 1-tridecanol, 1- Pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-octadecanol, 1
-Nonadecanol, 1-eicosanol, phenol,
Chlorophenol, benzyl alcohol, methyl cellosolve, or any mixture thereof, and the like can be mentioned. Preferably, 2-methyl-1-pentanol, 4-methyl-
1-pentanol, 4-methyl-2-pentanol, 2
-Ethyl-1-butanol, 2,4-dimethyl-3-ventanol, 2-ethyl-1-hexanol, 3,5-
Dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, 3,5-dimethyl-4-heptanol, 2,6-dimethyl-4-heptanol, 3,5
5-Trimethyl-1-hexanol and the like are desirable. Of course, various denatured alcohols called methanol-denatured alcohol and hexane-denatured alcohol which are commercially available as industrial alcohols can be used without any problem.

(6) The method for preparing a solid component containing titanium, magnesium and halogen as essential components is not particularly limited, and the above titanium compound and magnesium are prepared in the presence or absence of an inert hydrocarbon solvent. A method of co-milling a compound or the like at a temperature of 0 to 200 ° C. for 30 minutes to 50 hours using a ball mill, a vibration mill, a rod mill, an impact mill, or the like may be used.
Alcohols, phenols, ethers, ketones,
In an organic solvent composed of esters, amines, nitriles or the like or a mixture thereof, the mixture is heated and mixed at a temperature of 0 to 400 ° C., preferably 20 to 300 ° C. for 5 minutes to 10 hours, and then the solvent is removed by evaporation. A method may be used.
When the silicon oxide and / or aluminum oxide are added and allowed to react with each other, a method in which the reaction is carried out in an organic solvent is preferable, and when silicon oxide and / or aluminum oxide is not used, co-grinding is performed. Is preferred.

(7) The reaction ratio of each component is not particularly limited, but the Ti / Mg molar ratio is 0.001 to 100.
0, preferably 0.01 to 100, and more preferably 0.1 to 100.
It is desirable to use 05-10.

2. Examples of the organoaluminum compounds represented by the general formula AlR _n X _3-n to be used in the (II) component present invention, R is the number 1 to 24, preferably 1 to 12 alkyl group carbon atoms, an aryl group, A hydrocarbon group such as an aralkyl group, X is a bromine atom,
It indicates halogen such as chlorine atom and iodine atom,
And n represents n <n <3, preferably 1 ≦ n ≦ 2. Specific examples of these organoaluminum compounds include phenylaluminum chloride, diphenylaluminum chloride, benzylaluminum dichloride, dibenzylaluminum chloride, dimethylaluminum chloride, diethylaluminum fluoride, diethylaluminum chloride, diethylaluminum bromide, and diethylaluminum ion. Dyed, di-iso
Butylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquibromide, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride or any mixture thereof can be mentioned, in particular, diethylaluminum chloride, ethylaluminum Sesquichloride and ethylaluminum dichloride are preferred.

3. Component [III] The alkoxyaluminum compound represented by the general formula AlR _m (OR ′) _n X _{3- (m + n)} used in the present invention includes R
And R ′ are a hydrocarbon group such as an alkyl group, an aryl group, and an aralkyl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, which may be the same or different; X represents a halogen atom; m is 0 ≦ m <3, n is 0 <n ≦
3, 0 <m + n ≦ 3. Specific examples of these compounds include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, trin-propoxyaluminum, trin-butoxyalnium, triisobutoxyaluminum, trisec-
Butoxyaluminum, tri-t-butoxyaluminum, tri-n-pentoxyaluminum, tri-n-hexyloxyaluminum, tri-n-heptyloxyaluminum, tri-n-octyloxyaluminum, dimethoxyaluminum chloride, diethoxyaluminum chloride, diisopropoxyaluminum Chloride, di-n
-Propoxyaluminum chloride, di-n-butoxyaluminum chloride, diisobutoxyaluminum chloride, disec-butoxyaluminum chloride, dit
-Butoxyaluminum chloride, methoxyaluminum dichloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride, n-propoxyaluminum dichloride, n-butoxyaluminum dichloride, isobutoxyaluminum dichloride, sec
-Butoxyaluminum dichloride, t-butoxyaluminum dichloride, dimethoxyaluminum bromide, diethoxyaluminum bromide, diisopropoxyalnium bromide, din-propoxyaluminum bromide, din-butoxyaluminum bromide, diisobutoxyaluminum bromide, disec-butoxy Aluminum bromide, di-t-butoxyaluminum bromide, methoxyaluminum dibromide, ethoxyaluminum dibromide, isopropoxyaluminum dibromide, n-propoxyaluminum dibromide, n
-Butoxyaluminum dibromide, isobutoxyaluminum dibromide, sec-butoxyaluminum dibromide, t-butoxyaluminum dibromide, methyldimethoxyaluminum, methyldiethoxyaluminum, methyldiisopropoxyaluminum, methyldi-n-propoxyaluminum, methyldi-n- Butoxyaluminum, methyldiisobutoxyaluminum, methyldisec-butoxyaluminum, methyldit-butoxyaluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, ethyldiisopropoxyaluminum, ethyldin-propoxyaluminum,
Ethyldi-n-butoxyaluminum, ethyldiisobutoxyaluminum, ethyldisec-butoxyaluminum, ethyldit-butoxyaluminum, isobutyldimethoxyaluminum, isobutyldiethoxyaluminum, isobutyldiisopropoxyaluminum, isobutyldin-propoxyaluminum, isobutyldin-butoxyaluminum, Isobutyldiisobutoxyaluminum, isobutyldisec-butoxyaluminum, isobutyldit-butoxyaluminum, n-hexyldimethoxyaluminum, n-hexyldiethoxyaluminum, n-hexyldiisopropoxyaluminum, n-hexyldin-propoxyaluminum,
n-hexyldi-n-butoxyaluminum, n-hexyldiisobutoxyaluminum, n-hexyldisec
-Butoxyaluminum, n-hexyldi-t-butoxyaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, dimethylisopropoxyaluminum, dimethyl n-propoxyaluminum, dimethyln-butoxyaluminum, dimethylisobutoxyaluminum, dimethylsec-butoxyaluminum, dimethylt -Butoxyaluminum, diethylmethoxyaluminum, diethylethoxyaluminum, diethylisopropoxyaluminum, diethyl n-propoxyaluminum, diethyl n-butoxyaluminum, diethylisobutoxyaluminum, diethylse
c-butoxyaluminum, diethyl t-butoxyaluminum, diisobutylmethoxyaluminum, diisobutylethoxyaluminum, diisobutylisopropoxyaluminum, diisobutyl n-propoxyaluminum, diisobutyl n-butoxyaluminum, diisobutylisobutoxyaluminum, diisobutylse
c-butoxyaluminum, diisobutyl t-butoxyaluminum, di-n-hexylmethoxyaluminum,
Di-n-hexylethoxy aluminum, di-n-hexyl isopropoxy aluminum, di-n-hexyl n-propoxy aluminum, di-n-hexyl n-butoxy aluminum, di-n-hexyl isobutoxy aluminum,
Di-n-hexyl sec-butoxyaluminum, di-n-
Hexyl t-butoxyaluminum, methylmethoxyaluminum chloride, methylethoxyaluminum chloride, methylisopropoxyaluminum chloride, methyl n-propoxyaluminum chloride, methyl n-
Butoxyaluminum chloride, methylisobutoxyaluminum chloride, methyl sec-butoxyaluminum chloride, methyl t-butoxyaluminum chloride, ethylmethoxyaluminum chloride, ethylethoxyaluminum chloride, ethylisopropoxyaluminum chloride, ethyln-propoxyaluminum chloride, ethyln -Butoxyaluminum chloride,
Ethyl isobutoxy aluminum chloride, ethyl se
c-butoxyaluminum chloride, ethyl t-butoxyaluminum chloride, isobutylmethoxyaluminum chloride, isobutylethoxyaluminum chloride, isobutylisopropoxyaluminum chloride,
Isobutyl n-propoxyaluminum chloride, isobutyl n-butoxyaluminum chloride, isobutylisobutoxyaluminum chloride, isobutylsec
-Butoxyaluminum chloride, isobutyl t-butoxyaluminum chloride, n-hexylmethoxyaluminum chloride, n-hexylethoxyaluminum chloride, n-hexylisopropoxyaluminum chloride, n-hexyln-propoxyaluminum chloride, n-hexyln-butoxyaluminum chloride Chloride, n-hexylisobutoxyaluminum chloride,
n-hexyl sec-butoxyaluminum chloride,
n-hexyl t-butoxyaluminum chloride, methylmethoxyaluminum bromide, methylethoxyaluminum bromide, methylisopropoxyaluminum bromide, methyl n-propoxyaluminum bromide, methyl n-butoxyaluminum bromide, methylisobutoxyaluminum bromide, methylsec-butoxyaluminum Bromide, methyl t-butoxyaluminum bromide, ethylmethoxyaluminum bromide, ethylethoxyaluminum bromide, ethylisopropoxyaluminum bromide, ethyl n-propoxyaluminum bromide, ethyl n-butoxyaluminum bromide, ethylisobutoxyaluminum bromide, ethylsec-butoxyaluminum Bromide, ethyl t-butoxya Minium bromide, isobutyl methoxy aluminum bromide, isobutyl ethoxy aluminum bromide, isobutyl isopropoxy aluminum bromide, isobutyl n-propoxy aluminum bromide, isobutyl n-butoxy aluminum bromide, isobutyl isobutoxy aluminum bromide, isobutyl sec-butoxy aluminum bromide, isobutyl t-butoxy Aluminum bromide, n-hexyl methoxy aluminum bromide, n-hexyl ethoxy aluminum bromide, n-hexyl isopropoxy aluminum bromide, n-hexyl n-propoxy aluminum bromide, n-hexyl n-butoxy aluminum bromide, n-hexyl isobutoxy aluminum Bromide, n-hexyl sec-butyl Carboxymethyl aluminum bromide, n- hexyl t- butoxy aluminum bromide, and the like. Particularly, triethoxyaluminum, triisopropoxyaluminum, trisec
-Butoxyaluminum, disec-butoxyaluminum chloride, ethyldisec-butoxyaluminum, diethylsec-butoxyaluminum, ＄ ee-
Butoxyaluminum dichloride and ethyl sec-butoxyaluminum chloride are preferred. In addition, from the viewpoint of the reaction method at the time of obtaining the solid catalyst component, any of a solid state and a liquid state may be used, but preferably a liquid state when contacted with other components in view of a wide variation of the reaction method. It is desirable that

4. Production of Solid Catalyst Component In the present invention, the component [I] to obtain the solid catalyst component
The reaction order of the component [III] is as follows: (A) the component [I] and the component [II] are first reacted;
Thereafter, a method of reacting the component [III]. (B) A method of reacting the component [I] and the component [III] first, and then reacting the component [II]. (C) A method of reacting the component [II]. A method in which the component and the component (III) are reacted first, and then the component (I) is reacted. (D) A method in which the component (I) to the component (III) are simultaneously reacted. The method is not particularly limited, for example, pentane, cyclohexane, heptane, octane, nonane, decane, benzene,
In the presence or absence of a so-called inert hydrocarbon solvent which is inert to a general Ziegler catalyst such as toluene, xylene or the like, or a small amount of alcohol, ester, ketone, carboxylic acid or the like in these inert hydrocarbon solvents. A method of performing a reaction at a temperature of 0 to 300 ° C, preferably 20 to 150 ° C for 5 minutes to 10 hours, preferably a mixed reaction in the presence or absence of an electron donor compound such as an acid, an ether, an amine, and a phosphine is preferable. Used for In addition,
When the reaction is performed in the presence of an inert hydrocarbon solvent, it is preferable to remove the solvent after the reaction by means such as evaporation. Of course, when the component (I), the component (II) and the component (III) are allowed to react stepwise as in the reaction order of the above (A), (B) and (C), The reaction is carried out in the presence or absence of an inert hydrocarbon, respectively.For example, after the reaction in the presence of an inert hydrocarbon solvent in the first step, the reaction in the second step is performed after removing the solvent. That, after removing the solvent, to add a new solvent to perform the subsequent reaction, to perform the subsequent reaction without removing any solvent, and to add a new solvent to perform the subsequent reaction. Either way of doing is possible.

The reaction ratio of the component (I), the component (II) and the component (III) is as follows: component (II): component (II) / (titanium in component (I)) Component｝ (molar ratio) is 0.01 to 100, preferably 0.2
It is desirable to set it to 10 to 10, more preferably 0.5 to 5. The reaction ratio of the component (III) is
Component [III] / {Titanium component in component [I]}
(Molar ratio) is usually 0.01 to 10, preferably 0.03.
~ 5.0, more preferably 0.05 ~ 1.0. Each reaction operation relating to the preparation of the solid catalyst component should be performed in an inert gas atmosphere, and it is desirable to avoid moisture as much as possible.

<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 organic aluminum compounds of R ₃ Al ₂ X ₃ (where R is a hydrocarbon group such as an alkyl group or an aryl group having 1 to 20 carbon atoms, X is a halogen atom such as chlorine, bromine, iodine, etc.) Wherein R is the same or different, or R ₂ Zn (where R is 1 carbon atom)
-20, which may be the same or different), and are represented by trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Examples thereof include trisec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminumsexichloride, diethylzinc and a mixture thereof. The amount of the organometallic compound used is not particularly limited, but is usually 0.1 to 1000 mol based on the titanium compound.
It can be used 1 times. In the present invention, the organometallic compound component can also be preferably used as a mixture or an additional 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 per 1 mol of the organic metal compound.
1 mol, preferably 0.2 to 0.5 mol is used. When the compound is used as an addition compound of an organic metal compound and an organic acid ester, the molar ratio of the organic metal compound to the organic acid ester is preferably from 2: 1 to 1: 2.

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, dipropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate Cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl tritylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate,
cyclohexyl p-oxybenzoate, salicyl sampenzil, 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.

<3> Olefin Polymerization The olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization.
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.
℃, preferably 50 to 100 ℃, the pressure is 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, the hydrogen concentration,
The polymerization reaction in two or more different stages under different polymerization conditions such as the 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, such as ethylene, propylene,
Homopolymerization of α-olefins such as 1-butene, hexene-1, 4-methylpentene-1 and ethylene and propylene, ethylene and 1-butene, ethylene and hexene
1, copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms of ethylene such as 4-methylpentene-1, copolymerization of propylene and 1-butene, and copolymerization of ethylene with two or more other α-olefins It is suitably used for such purposes. Copolymerization with a diene for the purpose of modifying polyolefin is also preferably performed. Examples of the diene compound used at this time include butadiene, 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%.

[0019]

(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. Hexane extraction: The copolymer powder is roll-kneaded at 180 ° C., then pressed into a sheet of 5 cm × 5 cm × 0.2 mm, and extracted with hexane to extract the percentage of weight loss when it is extracted in boiling hexane for 5 hours. Amount. N value: using a Shimadzu flow tester (CFT-500), applying various loads to the material at 170 ° C., and setting the diameter to 2.0 ±
It is extruded from a die having a length of 0.01 mm and a length of 40.0 ± 0.01 mm, and a shear rate gradient with respect to a shear stress is calculated according to the following formula, and is set as an N value.

[0020]

(Equation 1)

Example 1 (a) Production of solid catalyst component 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 triethoxyaluminum were added. 4.2 g was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated 2-methyl-1-pentanol, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum, 10.0 g of ethoxy titanium was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour. Next, 3.5 g of trisec-butoxyaluminum was added and reacted at room temperature for 1.5 hours.
Nitrogen was blown at 3 ° C. for 3 hours to remove hexane 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 autoclave is formed by flowing hot water through a jacket. The temperature was adjusted. 80 ℃
The above solid catalyst component was added to the autoclave adjusted to 250.
mg / hr and 50 mmol of triethyl aluminum
1 / hr, while supplying each gas while adjusting the butene-1 / ethylene molar ratio in the autoclave gas phase to 0.35, and further adjusting the hydrogen to 15% of the total pressure. The gas in the system was circulated by a blower while keeping the pressure at 8 kg / cm ² G, and continuous polymerization was performed 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 1.05 g / 10 min, a density of 0.9202 g / cm ³ and a bulk density of 0.45 g.
/ Cm ³ and an average particle size of 820 μm. Further, the melting point of this copolymer was 121.5 ° C., the amount of hexane extracted was 2.2 wt%, and the n value was 1.44, and the molecular weight distribution was extremely narrow.

Example 2 (a) Production of solid catalyst component 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 triethoxyaluminum were added. 4.2 g was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated 2-methyl-1-pentanol, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum, 10.0 g of ethoxy titanium was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and tris
3.5 g of ec-butoxyaluminum was added and at room temperature.
The reaction was performed for 5 hours. Next, 10.0 g of diethylaluminum chloride was added and reacted at room temperature for 1 hour.
Nitrogen was blown at 3 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 240,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.01 g / 10
min, a density of 0.9198g / cm ^3, a bulk density of 0.44 g / cm ^3, was a round particulate matter having the shape of an average particle diameter of 840μm. The melting point of this copolymer was 122.1.
C., the amount of hexane extracted was 2.4 wt%, and the n value was 1.
45 and a very narrow molecular weight distribution.

Example 3 (a) Production of solid catalyst component 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, triethoxy aluminum 4.2 g was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated 2-methyl-1-pentanol, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum, 10.0 g of ethoxy titanium was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane, 10.0 g of diethylaluminum chloride and 3.5 g of trisec-butoxyaluminum were added, and the mixture was reacted at room temperature for 1.5 hours. Thereafter, nitrogen was blown at 70 ° C. for 3 hours to remove hexane and remove the solid. A catalyst component was obtained.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 230,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.98 g / 10
min, the density was 0.9201 g / cm ³ , the bulk density was 0.45 g / cm ³ , and the average particle diameter was 830 μm. The melting point of this copolymer is 121.8.
C., the amount of hexane extracted was 2.2 wt%, and the n value was 1.
44 and a very narrow molecular weight distribution.

Example 4 (a) Production of Solid Catalyst Component 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, triethoxy aluminum 4.2 g was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated 2-methyl-1-pentanol, 5.0 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum, 10.0 g of ethoxy titanium was added and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane, 10.0 g of diethylaluminum chloride and 2.2 g of triethoxyaluminum were added to a three-necked flask equipped with another stirrer and a reflux condenser, and the mixture was reacted at room temperature for 1 hour. The mixture was added to the solid powder and reacted at room temperature for 1.5 hours. Thereafter, nitrogen blowing was performed at 70 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 210,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.88 g / 10
min, the density was 0.9211 g / cm ³ , the bulk density was 0.45 g / cm ³ , and the average particle diameter was 790 μm. The melting point of this copolymer was 122.2.
C., the hexane extraction amount was 2.2 wt%, and the n value was 1.
45 and a very narrow molecular weight distribution.

Comparative Example 1 (a) Production of a solid catalyst component A stainless steel pot having a capacity of 400 ml and containing 25 stainless steel balls having a diameter of 1/2 inch was loaded with 10 g of commercially available anhydrous magnesium chloride and triethoxyaluminum. 4.2 g was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product.
A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, into which 100 g of dehydrated 2-methyl-1-pentanol, 5.0 g of a reaction product of the above anhydrous magnesium chloride and triethoxyaluminum, 10.0 g of tetra-n-ethoxytitanium was added and reacted at 80 ° C. for 1 hour.
After cooling to room temperature, 46 g of silica (Fuji Devison, # 955) calcined at 400 ° C. for 3 hours was added, reacted again at 80 ° C. for 2 hours, and dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next, 100 cc of dehydrated hexane and 10.0 g of diethylaluminum chloride were added, and reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 240,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.02 g / 10
min, the density was 0.9205 g / cm ³ , the bulk density was 0.45 g / cm ³ , and the average particle diameter was 830 μm. The melting point of this copolymer is 121.6.
C., the amount of hexane extracted was 2.7 wt%, the n value was 1.48, and the molecular weight distribution was wider than in Examples 1-4.

Example 5 (a) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and triethoxyaluminum 4 were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. In a nitrogen atmosphere, ball milling was performed at room temperature for 16 hours to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 cc of dehydrated ethanol, 17.0 g of dehydrated 2-ethyl-1-hexanol, and 15.0 g of tetra-n-butoxytitanium were placed therein, and the mixture was placed at room temperature. After stirring for 1 hour, 7.5 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum was added, and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Davison, # 955) calcined at 400 ° C. for 3 hours was added, and 80 g of
After reacting at 2 ° C. for 2 hours, the mixture was dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next 100 cc of dehydrated hexane
And 10.0 g of diethylaluminum chloride were added and reacted at room temperature for 1 hour. Then, 3.5 g of trisec-butoxyaluminum was added and reacted at room temperature for 1.5 hours.
Thereafter, nitrogen blowing was performed at 70 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 250,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.95 g / 10
min, a density of 0.9206 g / cm ³ , and a round granular material having a bulk density of 0.46 g / cm ³ and an average particle size of 840 μm. The melting point of this copolymer is 121.8.
C., the amount of hexane extracted was 2.0 wt%, and the n value was 1.
43 and a very narrow molecular weight distribution.

Example 6 (a) Production of solid catalyst component Commercially available 10 g of anhydrous magnesium chloride and triethoxyaluminum 4 were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. In a nitrogen atmosphere, ball milling was performed at room temperature for 16 hours to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 cc of dehydrated ethanol, 17.0 g of dehydrated 2-ethyl-1-hexanol, and 15.0 g of tetra-n-butoxytitanium were placed therein, and the mixture was placed at room temperature. After stirring for 1 hour, 7.5 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum was added, and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Davison, # 955) calcined at 400 ° C. for 3 hours was added, and 80 g of
After reacting at 2 ° C. for 2 hours, the mixture was dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next 100 cc of dehydrated hexane
And 3.5 g of trisec-butoxyaluminum were added and reacted at room temperature for 1 hour. Next, 10.0 g of diethylaluminum chloride was added and reacted at room temperature for 1.5 hours. Thereafter, nitrogen blowing was performed at 70 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Gas phase polymerization Polymerization was carried out under the same conditions as in Example 1 using the above solid catalyst component. The catalyst efficiency is 240,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 0.89 g / 10
min, a density of 0.9208 g / cm ³ , and a round granular material having a bulk density of 0.45 g / cm ³ and an average particle size of 880 μm. The melting point of this copolymer was 122.5.
C., hexane extraction amount was 2.5 wt%, and n value was 1.
45 and a very narrow molecular weight distribution.

COMPARATIVE EXAMPLE 2 (a) Production of Solid Catalyst Component 10 g of commercially available anhydrous magnesium chloride and triethoxyaluminum 4 were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. In a nitrogen atmosphere, ball milling was performed at room temperature for 16 hours to obtain a reaction product. A three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 140 cc of dehydrated ethanol, 17.0 g of dehydrated 2-ethyl-1-hexanol, and 15.0 g of tetra-n-butoxytitanium were placed therein, and the mixture was placed at room temperature. After stirring for 1 hour, 7.5 g of the above-mentioned reaction product of anhydrous magnesium chloride and triethoxyaluminum was added, and reacted at 80 ° C. for 1 hour. After cooling to room temperature, 46 g of silica (Fuji Davison, # 955) calcined at 400 ° C. for 3 hours was added, and 80 g of
After reacting at 2 ° C. for 2 hours, the mixture was dried under reduced pressure at 120 ° C. for 2 hours to obtain a solid powder. Next 100 cc of dehydrated hexane
Then, 10.0 g of diethylaluminum chloride was added, and the mixture was reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 60 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

When the polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, the catalyst efficiency was 280,00.
0g copolymer / gTi and high activity, MFR 0.87g /
It was a round granular material having a density of 0.9210 g / cm ³ , a bulk density of 0.45 g / cm ³ , and an average particle size of 880 μm for 10 min. The melting point of this copolymer was 121.
At 8 ° C., the hexane extraction amount was 2.9 wt%, and 1.49.
And Examples 5 and 6, the molecular weight distribution was wider.

Example 7 (a) Production of Solid Catalyst Component 10 g of anhydrous magnesium chloride and triethoxyaluminum 4 were placed in a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch. .2 g and titanium tetrachloride were added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen.
g, 100 cc of dehydrated hexane and 4.6 g of getyl aluminum chloride were added and reacted at room temperature for 1 hour. Next, 1.0 g of trisec-butoxyaluminum was added and reacted at room temperature for 1.5 hours. Thereafter, nitrogen blowing was performed at 70 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Slurry polymerization A 21-volume stainless steel autoclave equipped with an electromagnetic induction stirrer was thoroughly dried, and dried hexane 10
00 ml, 1 mmol of triethylaluminum and 10 mg of the above solid catalyst component were added. After raising the internal temperature to 70 ° C. and adding 3 kg / cm ^{2 of} hydrogen, ethylene was pressurized to 10 kg / cm ² together with 10 g of 1-butene to initiate polymerization. Polymerization was carried out for 2 hours by continuously pressurizing ethylene at 10 kg / cm ² , and then methanol was added to stop the polymerization, hexane was removed by evaporation and white polyethylene powder 95 was removed.
g was obtained. The catalyst efficiency is 240,000 g copolymer / gT
i and very high activity. The produced ethylene copolymer had a melt flow rate (MFR) of 1.22 g / 10
min, the density was 0.9223 g / cm ³ , and the bulk density was 0.38 g / cm ³ . Further, the melting point of this copolymer was 122.5 ° C., the hexane extraction amount was 2.15 wt%, and the n value was 1.43, and the molecular weight was extremely narrow.

COMPARATIVE EXAMPLE 3 (a) Production of Solid Catalyst Component 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 triethoxyaluminum 4 .2 g and titanium tetrachloride were added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder. The three-necked flask equipped with a stirrer and a reflux condenser was purged with nitrogen.
g, 100 cc of dehydrated hexane and 4.6 g of diethylaluminum chloride were added, and reacted at room temperature for 1 hour. Thereafter, nitrogen blowing was performed at 70 ° C. for 3 hours to remove hexane to obtain a solid catalyst component.

(B) Slurry polymerization Using the above solid catalyst component, the same polymerization as in Example 7 was carried out to obtain 105 g of a white polyethylene powder. The catalyst efficiency was as high as 260,000 g copolymer / gTi. The produced ethylene copolymer had a melt flow rate (MFR) of 1.32 g / 10 min and a density of 0.9.
215 g / cm ³ and a bulk density of 0.35 g / cm ³
Met. The melting point of this copolymer was 122.4 ° C., the amount of hexane extracted was 3.45 wt%, and the n value was 1.50.
And the molecular weight distribution was wider as compared with Example 7.

[0041]

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, and a narrow particle size distribution. Because there are few fine powder parts,
Stable operation is possible with little adhesion of the polymer to the reactor wall during polymerization, and furthermore, the generation of dust during the molding process can be prevented, and the efficiency during the molding process can be increased. Can also be omitted. Further, since the polymer has a narrow molecular weight distribution, 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.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-248705 (JP, A) JP-A-58-1705 (JP, A) JP-A-3-153707 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid catalyst component and an organoaluminum compound
Alternatively, in a method of polymerizing or copolymerizing an olefin using an organozinc compound as a catalyst, the solid catalyst component comprises [I] at least a magnesium source represented by the general formula MgX
₂ (where X represents a halogen atom)
Titanium, magnesium and a halogen solids [II] by formula AlR _n X _3-n (here, containing as essential components, R represents indicates a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, respectively, n Is an organic aluminum compound represented by 0 <n <3), and [III] a general formula AlR _m (OR ′) _n X _{3- (m + n)} (where R and R ′ each have 1 carbon atom ₎ To 24 hydrocarbon groups which may be the same or different, X represents a halogen atom, m is 0 ≦ m <3, n is 0 <n ≦ 3, 0 <m
+ N ≦ 3). A method for producing a polyolefin comprising a substance obtained by mutually reacting alkoxyaluminum compounds represented by the formula: