JPH06322026A - Production of polyolefin - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a method for producing a highly flowable polyolefin having a high bulk density, a narrow particle size distribution, a remarkably small amount of fine particles of a polymer, and a high fluidity. [Structure] SiO ₂ or Al ₂ O ₃ and Ti or Ti / V
The product [1] obtained by reacting a compound and then reacting it with an organoaluminum compound, MgX ₂ and Me (O ₂
R) _n X _z-n (Me = I to IV group, X = halogen, z
= Me valence, 0 <n ≦ z) and Ti or T as desired
The reaction product [2] with an i / V compound is reacted with a compound [3] having a Si—N—C or Si—O—C bond, which is used as a solid catalyst component. An Al compound and a compound having a Si—N—C or Si—O—C bond are combined to form a catalyst system for olefin polymerization.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a novel polyolefin. More specifically, the present invention significantly increases the polymer yield per solids and the polymer yield per transition metal, thereby eliminating the step of removing catalyst residues in the polymer, and the bulk of the resulting polymer. The present invention relates to a method of increasing the density and reducing the finely powdered 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]

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

The inventors of the present invention have previously found a new catalyst component that has improved the above-mentioned drawbacks, and have already filed various patent applications (Japanese Patent Publication No. 11651/1989, Japanese Patent Publication No. 12289/1988).
0-149605, JP 62-32105, JP 6
2-207306). When 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 directly apply the powder polymer to a processing machine. It was

On the other hand, among the applications of polyolefin, there are many fields in which a polymer having a narrow molecular weight distribution is required.
For example, injection molding grade improves impact strength,
Further, in the film grade, it is necessary to narrow the molecular weight distribution in order to improve the strength, transparency, anti-blocking property and heat sealing property.

The present inventors have previously found a new 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, Japanese Patent Application No. 2-179485, etc.). When using this catalyst component,
Although the molecular weight distribution was narrowed and it was possible to improve the product characteristics, further improvement is necessary.

The present invention solves these problems by making a polymer having a higher bulk density, a narrow particle size distribution, a remarkably small amount of fine particles of the polymer, a good fluidity and a narrow molecular weight distribution, and having a very high activity. The present invention has been achieved as a result of intensive research aimed at obtaining the same.

[0007]

Means for Solving the Problems That is, according to the present invention, [I] a reaction product of the following (1) and a reaction product of the above (2) are first reacted to give the reaction product of the reaction product of (3). Solid catalyst component obtained by the reaction; (1) a) silicon oxide and / or aluminum oxide and b) titanium compound or a reaction product obtained by reacting a titanium compound and a vanadium compound. the reaction product obtained by reacting, (2) b) magnesium halide and ii) the general formula _{Me (oR) n X z-} n ( wherein Me periodic table I~IV elements of group, z is an element M
a valence of e, n is 0 <n ≦ z, X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, and a reaction product obtained by reacting the compound and (3 ) Silicon compounds having at least one Si-O-C bond and / or at least one Si-N-C bond, [II] at least one Si-O-C bond and / or at least-Si-N-C bond. The present invention relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin with a catalyst system in which a silicon compound having a bond and [III] an organometallic compound are combined.

The present invention further provides [I] a solid catalyst obtained by first reacting the reaction product of (1) below with the reaction product of (2) and then reacting the reaction product of (3) with the reaction product. Components: (1) a) silicon oxide and / or aluminum oxide and b) reaction obtained by reacting a titanium compound or a titanium compound and a vanadium compound with c) an organoaluminum compound. Product, (2) a) magnesium halide and b) general formula Me (OR) _n X _z-n (where Me is an element of Group I to IV of the periodic table, and z is an element M).
the valence of e, n is 0 <n ≦ z, X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, and c) a titanium compound or a titanium compound and a vanadium compound And a reaction product obtained by reacting (3) a silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond, [II] at least one Si—O—C The present invention relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin with a catalyst system comprising a combination of a silicon compound having a bond and / or at least one Si—N—C bond and [III] an organometallic compound.

By using the method of the present invention, a polyolefin having a relatively large average particle size, a narrow particle size distribution, and a small amount of fine particles can be obtained with extremely high activity, and the bulk specific gravity of the produced polyolefin is high and free flowing. It is very advantageous in polymerization operation, such as good properties, and it can be used for molding processing not only when it is used as pellets but also in powder form, there are few troubles during molding processing, and it is extremely advantageous to manufacture polyolefin can do.

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

The present invention will be specifically described below.

The catalyst used in the method for producing a polyolefin of the present invention is [I] (1) a) silicon oxide and / or aluminum oxide, (component [I]-(1) -a)) and b) titanium. The reaction product obtained by reacting a compound or a titanium compound with a vanadium compound (component [I]-(1) -ro)) is further mixed with an organic aluminum compound (component [I]-(1)-).
A reaction product obtained by reacting (c)) with (2) a) magnesium halide (component [I]-
(2) -a)) and b) General formula Me (OR ¹ ) _n X _z-n (where Me is an element of Group I to IV of the periodic table, and z is an element M).
the valence of e, n is 0 <n ≦ z, X is a halogen atom, R ¹
Represents a hydrocarbon residue having 1 to 20 carbon atoms) (a component [I]-(2) -ro)), and a reaction product obtained by reacting the same is further optionally titanium) titanium. Compounds or substances obtained by reacting titanium compounds with vanadium compounds (component [I]-(2)-
A reaction product obtained by reacting c)), and (3) a silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond is reacted with the reaction product. The solid catalyst component (component [I]) thus obtained and [II] a silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond (component [II] component) [ III] Organometallic compound (Component [III]).

1. Solid Catalyst Component (Component [I]) (1) Silicon Oxide (Component [I] Used in the Present Invention
-(1) -a)) is a complex oxide of silica or silicon and at least one other metal of Group I to VIII of the periodic table.

The aluminum oxide used in the present invention is alumina or aluminum and the periodic table I to VI.
It is a complex oxide with at least one other metal of Group II.

Silicon or Aluminum and Periodic Table I
Typical examples of the complex oxide with at least one other metal of Group VIII are Al ₂ O ₃ .MgO and 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 O ₃ .Ni
Examples thereof include various natural or synthetic complex oxides such as O and SiO ₂ .MgO. Here, the above formula is not a molecular formula, but represents only the composition, and the structure and the component ratio of the composite oxide used in the present invention are not particularly limited.

As a matter of course, the silicon oxide and / or aluminum oxide used in the present invention can be used even if it absorbs a small amount of water, and can be used without any problem even if it 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, but the particle size is preferably 1-2.
00 μm, pore volume 0.3 ml / g or more, surface area 5
Silica of 0 m ² / g or more is desirable. Before use, it is desirable to perform firing treatment at 200 to 800 ° C. in advance by a conventional method.

The titanium compound or titanium compound and vanadium compound (component [I] -1-B)) to be brought into contact with silicon oxide and / or aluminum oxide is titanium or a halide of titanium and vanadium. Alkoxy halide, alkoxide, Examples thereof include halogenated oxides. 4 as a titanium compound
Valent titanium compounds and trivalent titanium compounds are preferred,
Specific examples of the tetravalent titanium compound include the general formula Ti (O
R) _n X _4-n (wherein R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, X represents a halogen atom, and n is 0 ≦ n ≦ 4). Preferred are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichloro. Titanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxymonochlorotitanium. , Tetrabutoxytitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium and the like.

The trivalent titanium compound is obtained by reducing titanium tetrahalide such as titanium tetrachloride or titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of Group I to III metal of the periodic table. Examples include titanium trihalides. Further, the general formula Ti (OR) _m X _4-m
(Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and X represents a halogen atom.
m is 0 <m ≦ 4. ) A trivalent titanium compound obtained by reducing a tetravalent halogenated alkoxytitanium or tetraalkoxytitanium represented by) with an organometallic compound of a metal of Group I to III of the periodic table. Among these titanium compounds, titanium tetrahalide is particularly preferable.

Examples of the vanadium compound include pentavalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. . Further, it is often performed to use a titanium compound and a vanadium compound in combination. At this time, the V / Ti molar ratio is 2/1 to 0.01 / 1.
Is preferred.

Component [I]-(1) -a) and component [I]-
The reaction ratio with (1)-(b) is component [I]-(1) -a)
Component [I]-(1) -a) per 1 g of component [I]-
(1) -B) 0.01 to 10.0 mmol, preferably 0.1 to 5.0 mmol, more preferably 0.2 to
It is desirable to react with 2.0 mmol.

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.
When heat mixing is performed at 300 ° C., preferably 50 to 150 ° C. for 5 minutes to 10 hours, or component [I]-(1)-
It is desirable to obtain a reaction product by directly contacting (i) with component [I]-(1) -b) in the absence of an inert hydrocarbon.

The component [I]-(1) -a) and the component [I]-(2) -b) may be contact-reacted and then washed with an inert hydrocarbon several times. In addition, the component [I]-
After the catalytic reaction of (1) -a) with the component [I]-(2) -b), the inert hydrocarbon may be removed by evaporation. You may proceed to a contact reaction process.

[0024] Organic aluminum compounds used in the present invention (component [I] - (1) - c) The), general formula AlR _n X _3-n (wherein R 1 to 24 carbon atoms,
Preferably, 1 to 12 hydrocarbon groups such as an alkyl group, an aryl group and an aralkyl group, X represents halogen, and n is 0 <
n ≦ 3) is preferable, and specifically, phenyl aluminum dichloride, diphenyl aluminum chloride, benzyl aluminum dichloride, dibenzyl aluminum chloride, dimethyl aluminum chloride, diethyl aluminum fluoride, diethyl. Aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride or any mixture thereof, and the like. Can be, especially, diethylaluminium chloride, ethylaluminium Musesukikurorido, ethylaluminum dichloride are preferred.

Component [I]-(1) -a) and component [I]-
The reaction ratio of the contact product of (1) -b) and the organoaluminum compound (component [I]-(1) -ha) is the same as that of the component [I].
-(1) -C) / Component [I]-(1) -B) (molar ratio)
Is 0.1 to 100, preferably 0.2 to 10 and more preferably 0.5 to 5.

Components [I]-(1) -a) and [I]-
(1) -B) contact product and component [I]-(1) -C)
The method of reacting with is not particularly limited, but specifically, component [I]-(1) -i) and component [I]-(1)-
In the presence of an inert hydrocarbon solvent (described later) obtained by sufficiently dehydrating the contact product of (b) and the component [I]-(1) -ha), the temperature is 20 to 300 ° C, preferably 50 to 150 ° C.
After heating and mixing for 5 minutes to 10 hours to bring them into contact with each other, and after the completion of the reaction, the unreacted organoaluminum compound is removed by washing with an inert hydrocarbon several times,
A method of evaporating and removing the inert hydrocarbon can be exemplified.

(2) As the magnesium halide (component [I]-(2) -a) used in the present invention, a substantially anhydrous one is used. Magnesium fluoride, magnesium chloride, magnesium bromide , And magnesium iodide, and magnesium chloride is particularly preferable.

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

The general formula Me (OR ¹ ) used in the present invention
_n X _z-n (where Me is an element of Group I to IV of the periodic table,
z represents the valence of the element Me, n represents 0 <n ≦ z, and X represents a halogen atom. R ¹ has 1 to 20 carbon atoms, preferably 1
To 8 are hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, which may be the same or different) (component [I]-(2) -ro))
Are, for example, NaOR, Mg (OR) ₂ , Mg
(OR) X, Ca (OR) ₂ , Zn (OR) ₂ , Cd
(OR) ₂ , B (OR) ₃ , Al ((OR) ₃ , Al
(OR) ₂ X, Al (OR) X ₂ , Si (OR) ₄ , S
i (OR) ₃ X, Si (OR) ₂ X ₂ , Si (OR) X
Various compounds represented by ₃ , ₃ , Sn (OR) _{4, and the} like can be given. Preferred examples of these include M
g (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 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)
Compounds such as ₄ can be mentioned.

Component [I]-(2) -a) and component [I]-
The reaction ratio with (2) -b) is such that the component [I]-(2)-
B) / component [I]-(2) -i) (molar ratio) is 0.01
The range of -10, preferably 0.1-5 is desirable.

Component [I]-(2) -a) and component [I]-
The method of reacting with (2) -b) is not particularly limited, and both are in the presence or absence of an inert hydrocarbon solvent at a temperature of 0 to 200 ° C. for 30 minutes to 50 hours, a ball mill, A method of co-grinding using a vibration mill, a rod mill, an impact mill or the like may be used, and an inert hydrocarbon, alcohols, phenols, ethers, ketones, esters, amines, nitriles, etc., or A method may be used in which both of them are mixed and heated in an organic solvent consisting of a mixture at a temperature of 20 to 400 ° C., preferably 50 to 300 ° C. for 5 minutes to 10 hours, and then the solvent is removed by evaporation. In the present invention, a method of co-milling both is preferably used.

In order to make the present invention more effective, a reaction product of the component [I]-(2) -i) and the component [I]-(2) -b) and further a titanium compound or a titanium compound and vanadium. A compound (component [I]-(2) -ha)) can also be used in combination. The titanium compound to be used in combination is specifically selected from various titanium compounds and vanadium compounds used as the above-mentioned component [I]-(1) -b), and the component [I]-(1) -B) may be the same or different compound, but is preferably a compound represented by the general formula Ti (OR) _n X _4-n (wherein R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group) X is a halogen atom, and n is 0 ≦ n ≦ 4), and titanium tetrachloride is particularly preferable.

The amount of the titanium compound or the titanium compound and the vanasimu compound used in combination is the same as the amount of the component [I]-
The ratio of (2)-(c) / component [I]-(2) -i) (molar ratio) is 0.01 to 1, preferably 0.05 to 0.5.

In addition to the components [I]-(2) -a) and the components [I]-(2) -b), the components [I]-(2) -b) are further added.
The contact method in the case of using (c) together is not particularly limited, but specifically, component [I]-(2) -a), component [I]-(2) -b) and component [I]-(). 2) -C)
It may be either a method of simultaneously contacting with each other or a method of contacting each component in an arbitrary order, but preferably the component [I]-
(2) -a), component [I]-(2) -b) and component [I]-(2) -ha) are contacted simultaneously, or component [I]-(2) -a) and component [I]-(2)-
After contacting (b) in advance as described above, the component [I]-
The method of contacting (2) -C) is desirable. Specifically, these three components are simultaneously used, or the component [I]-(2)-
The reaction product of (a) with component [I]-(2) -b) and component [I]-(2) -ha) in the presence or absence of a hydrocarbon solvent inert to the Ziegler catalyst; Temperature 0-200
A method of co-milling for 30 minutes to 50 hours at a temperature of 30 minutes to 50 hours using a ball mill, a vibration mill, a rod mill, an impact mill or the like may be used, and the presence or absence of an inert hydrocarbon solvent for the Ziegler catalyst may be used. You may use the method of carrying out a mixed heating reaction in the presence of 20 to 300 ° C., preferably 50 to 150 ° C. for 5 minutes to 10 hours, and then removing the solvent by evaporation.

In the present invention, a method of co-milling both is preferably used.

(3) At least one S in the silicon compound (component [I]-(3)) used in the present invention.
The i-O-C bond compound having the general formula _{^{R 1 a R 2 b R 3}} c Si (OR 4) d X
_{4- (a + b + c + d)} (wherein R ¹ , R ² , R ³ and R ⁴ have 1 to 2 carbon atoms)
0, preferably hydrogen or a chain saturated hydrocarbon group such as an alkyl group of 1 to 12, an alicyclic hydrocarbon group such as a cycloalkyl group, an aromatic hydrocarbon group such as an aryl group and an aralkyl group, and a crosslinked hydrocarbon group. And the like, which may be the same or different from each other. X represents a halogen atom such as chlorine, bromine or iodine, or hydrogen, and a, b, c and d are 0 ≦ a <4, 0 ≦ b <4,0.
≦ c <4, 0 <d <4 and 0 <a + b + c <4, 1
<A + b + c + d ≦ 4). Examples of these compounds include R ¹ Si (OR ² ) ₃ and R ¹ Si (O
R ² ) ₂ X, R ¹ Si (OR ² ) X ₂ , R ¹ R ² Si
(OR ³ ) ₂ , R ¹ R ² Si (OR ³ ) X, R ¹ R ² R
Examples thereof include various compounds represented by ³ Si (OR ⁴ ).

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

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

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

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

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

(CH ₃ ) ₂ Si (OCH ₃ ) Cl, (C
_{H 3) 2 Si (OC 2} H 5) Cl, (C 2 H 5) 2 Si
_{(OCH 3) Cl, (C} 2 H 5) 2 Si (OC 2 H 5)
_{Cl, (i-C 3 H} 7) 2 Si (OCH 3) Cl, (i
_{-C 3 H 7) 2 Si (} OC 2 H 5) Cl, (t-C 4 H
₉ ) ₂ Si (OCH ₃ ) Cl, (t-C ₄ H ₉ ) ₂ Si
(OC ₂ H ₅ ) Cl, (PH) ₂ Si (OCH ₃ ) C
1, (PH) ₂ Si (OC ₂ H ₅ ) Cl, (CyH) ₂
Si (OCH ₃ ) Cl, (CyH) ₂ Si (OC
₂ H ₅ ) Cl, (CH ₃ ) (t-C ₄ H ₉ ) Si (OC
_{H 3) Cl, (CH 3} ) (t-C 4 H 9) Si (OC 2
H ₅ ) Cl, (CH ₃ ) (PH) Si (OCH ₃ ) C
1, (CH ₃ ) (PH) Si (OC ₂ H ₅ ) Cl, (C
_{H 3) (CyH) Si (} OCH 3) Cl, (CH 3)
(CyH) Si (OC ₂ H ₅ ) Cl, (PH) ₂ Si
_{(Oi-C 3 H 7)} Cl, (CyH) 2 Si (Oi-C
₃ H ₇ ) Cl, (CH ₃ ) (t-C ₄ H ₉ ) Si (Oi
_{-C 3 H 7) Cl, (} CH 3) (PH) 2 Si (Oi-
_{C 3 H 7) Cl, (} CH 3) (CyH) 2 Si (Oi-
_{C 3 H 7) Cl, (} CH 3) 3 Si (OCH 3), (C
_{H 3) 3 Si (OC 2} H 5), (C 2 H 5) 3 Si (O
_{CH 3), (C 2 H} 5) 3 Si (OC 2 H 5), (CH
_{3) 2 (t-C 4} H 9) Si (OCH 3), (CH 3)
_{2 (t-C 4 HG)} Si (OC 2 H 5), (CH 3) 2
_{(PH) Si (OCH 3)} , (CH 3) 2 (PH) Si
(OC ₂ H ₅ ), (CH ₃ ) ₂ (CyH) Si (OCH
_3), it may be mentioned _{(CH 3) 2 (CyH)} Si (OC 2 H 5), compounds such as.

The silicon compound having at least one Si--N--C bond used in the present invention is represented by the general formula R ⁵ _a R ⁶ _b R ⁷ _c Si (NR ⁸ ₂ ) _d X
_{4- (a + b + c + d)} (wherein R ⁵ , R ⁶ , and R ⁷ are hydrogen or 1 to 2 carbon atoms)
0, preferably hydrogen or a hydrocarbon residue such as 1 to 12 alkyl group, aryl group, aralkyl group, etc., R ⁸ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, aryl group, aralkyl group A hydrocarbon residue of 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, X represents a halogen atom such as fluorine, chlorine, bromine and iodine or a hydrogen atom, and a, b, c and d are 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, Si {N (C 2 H 5) 2}
₄ , HSi {N (CH ₃ ) ₂ } ₃ , HSi {N (C ₂ H
₅ ) ₂ } ₃ , CH ₃ Si {N (CH ₃ ) ₂ } ₃ , CH _{3
Si {N (C 2 H 5} ) 2} 3, C 2 H 5 Si {N (CH
₃ ) ₂ } ₃ , C ₂ H ₅ Si {N (C ₂ H ₅ ) ₂ } ₃ , C
₃ H ₇ Si (N (CH ₃ ) ₂ } ₃ , C ₃ H ₇ Si {N
_{(C 2 H 5) 2}} 3, C 4 H 9 Si {N (CH 3) 2}
₃ , C ₄ H ₉ Si {N (C ₂ H ₅ ) ₂ } ₃ , C ₆ H ₅ S
_{i {N (CH 3) 2} } 3, C 6 H 5 Si {N (C
_{2 H 5) 2} 3,} C 2 H 4 Si {N (CH 3) 2} 3,
_{C 2 H 4 Si {N (} C 2 H 5) 2} 3,

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

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

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

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

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

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

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

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

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

Si {NH (CH ₃ )} ₃ Cl, Si {N
H (C ₂ H ₅ )} ₃ Cl, HSi {NH (CH ₃ )} ₂
Cl, HSi {NH (C ₂ H ₅ )} ₂ Cl, CH ₃ Si
{NH (CH ₃ )} ₂ Cl, CH ₃ Si {NH (C ₂ H
₅ )} ₂ Cl, C ₂ H ₅ Si {NH (CH ₃ )} ₂ C
l), 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 {N
H (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

[0056]

[Chemical 1]

[0057]

[Chemical 2]

A silicon compound having an equicyclic amino group can also be used.

Among these compounds, (CH ₃ ) ₂ Si
(OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si (OC
₂ H ₅ ) ₂ , (PH) ₂ Si (OCH ₃ ) ₂ , (C
_{H 3) 2 Si (OC 2} H 5) 2, (CH 3) (t-C 4
_{H 9) Si (OCH 3)} 2, (CH 3) (CyH) Si
(OCH ₃ ) ₂ , Si {N (CH ₃ ) ₂ } ₄ , CH ₃ S
_{i {N (CH 3) 2} } 3, 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 , (CH ₃ ) ₂ Si
{N (C ₂ H ₅ ) ₂ } ₂ and the like are particularly preferable.

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

(4) In the present invention, the solid catalyst component is obtained by first reacting the components [I]-(1) and [I]-(2),
Then, it is obtained by catalytically reacting the component [I]-(3).

The reaction ratio of [I]-(1) and [I]-(2) is [I]-(2) per 1 g of [I]-(1) -a).
-A) is 0.01 to 20.0 mmol, preferably 0.1.
1 to 10 mmol, more preferably 0.2 to 4.0 m
It is desirable to set it to mol.

The reaction ratio of the reaction product of [I]-(1) and [I]-(2) and [I]-(3) is [I]-(3) /
([I]-(1) -ro) + [I]-(2) -ha)) (molar ratio) is 0.01 to 10, preferably 0.03 to 5, and more preferably 0.05 to 1. Is desirable.

The reaction method of [I]-(1) and [I]-(2) is not particularly limited, and the temperature is from 0 to 200.
Co-grinding treatment may be performed at 30 ° C. for 30 minutes to 50 hours, and an inert hydrocarbon, alcohols, phenols, ethers, ketones, esters, nitriles,
A method of mixing and heating in an organic solvent composed of amines or a mixture thereof at a temperature of 50 to 300 ° C. for 1 minute to 48 hours and then removing the solvent may be used, and preferably in an organic solvent. A method of removing the organic solvent after the treatment is desirable.

The reaction method of the reaction product of [I]-(1) with [I]-(2) and [I]-(3) is not particularly limited, and the reaction is carried out by co-grinding treatment. Alternatively, the reaction may be carried out in the presence or absence of an inert hydrocarbon solvent. The reaction at this time is desirably carried out under heating at a temperature of 0 to 300 ° C., preferably 20 to 150 ° C. for 5 minutes to 20 hours.

Of course, [I]-(1), [I]-
The operations for preparing (2), [I]-(3) and the solid catalyst component should be carried out in an inert gas atmosphere,
Moisture should be avoided as much as possible.

[I]-(1), [I]-of the present invention
The various organic solvents used in the preparation of (2), [I]-(3) and the preparation of the solid catalyst component are as follows.

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

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

Further, the ether used is represented by the following general formula: R—O—R ′ (where R and R ′ are hydrocarbon residues such as an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group and an aralkyl group). Groups, which may be the same or different, may be an organic residue containing oxygen, nitrogen, sulfur, chlorine, and other elements, and R and R'form a ring. The compound represented by (1) may be preferably used, and specific examples thereof include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, taylahydrofuran, dioxane, anisole and the like. Moreover, you may use these as a mixture.

As the above-mentioned ketone to be used,

[0072]

[Chemical 3]

(Wherein R and R'represent a hydrocarbon residue such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group having 1 to 20 carbon atoms, which may be the same or different. These are oxygen, It may be an organic residue containing nitrogen, sulfur, chlorine, or other elements, and R and R'may form a ring). Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone and cyclohexanone. Moreover, you may use these as a mixture.

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

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

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

Thus, [I]-(1) and [I]-
(2) is catalytically reacted, and then [I]-(3) is catalytically reacted to obtain a solid catalyst component.

Such a solid powder can be directly used as a solid catalyst component in the production of polyolefin and has sufficient performance. However, the solid component is used as the component [I]-(1).
The effect of the present invention can be further enhanced by carrying out contact treatment with various organoaluminum compounds used as (iii) and then using as a solid catalyst component.
The organoaluminum compound used here is a component [I]-
The compound may be the same as or different from (1)-(c).

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

The contact reaction ratio of the organoaluminum compound at this time is as follows: organoaluminum compound / {[I]
-(1) -B) + [I]-(2) -C) (arbitrary component)}
(Molar ratio) is 0.1 to 100, preferably 0.2 to 1
It is preferable to set it to 0, more preferably 0.5 to 5.

2. Silicon Compound (Component [II]) As the silicon compound as the component [II] used in the present invention, the same compounds as the compounds [I]-(3) can be mentioned.

Among these compounds, Si (OC
_{H 3) 4, Si (OC} 2 H 5) 4, (CH 3) 2 Si
(OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si (OC
₂ H ₅ ) ₂ , (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , (C
_{2 H 5) 2 Si (OCH} 3) 2, (CH 3) HSi (O
CH ₃ ) ₂ , (C ₂ H ₅ ) HSi (OCH ₃ ) ₂ , (C
_{H 3) HSi (OC 2 H} 5) 2, (C 2 H 5) HSi
(OCH ₃ ) ₂ , HSi (OCH ₃ ) ₃ , HSi (OC
₂ H ₅ ) ₃ , HCH ₃ Si {N (CH ₃ ) ₂ } ₂ , HC
_{H 3 Si {N (C 2} H 5) 2} 2, (CH 3) 2 Si
{N (CH ₃ ) ₂ } ₂ , (CH ₃ ) ₂ Si {N (C ₂ H
₅ ) ₂ } ₂ and the like are particularly preferable.

In the present invention, the amount of the silicon compound (component [II]) used is as follows: component [II] / {component [I]-(1) -II) + component [I in component [I]] ]
-(2) -ha)} (molar ratio) is preferably 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 and the silicon compound, and an organometallic compound, and the organometallic compound is a periodic table known as a component of a Ziegler catalyst. Organometallic compounds of Groups 1 to IV can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include general formulas R ₃ Al and R ₂ Al.
X, RAlX ₂ , R ₂ AlOR, RAl (OR) X and R ₃ Al ₂ X ₃ organoaluminum compounds (provided that 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, iodine, or bromine, R may be the same or different) or the general formula R ₂ Zn ( However, R is an alkyl group having 1 to 20 carbon atoms and may be the same as or different from each other.
Triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum,
Diethyl aluminum chloride, diisopropyl aluminum chloride, ethyl aluminum sex chloride,
Examples include diethyl zinc and mixtures thereof.

In the present invention, the amount of the organometallic compound (component [III]) used is not particularly limited, but it is usually
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]), the silicon compound (component [II]) and the organometallic compound (component [III]) are supplied to the polymerization reactor as a method. Is not particularly limited, but the first [I]
Component, [II] component and [III] component are separately supplied, or [II] component and [II] component
It is desirable to supply the mixture of the component [I] and the component [I] separately.

In the present invention, the organometallic compound component may be preferably used as a mixture or an addition compound of the organometallic compound and the 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 usually used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol, relative to 1 mol of the organic metal compound. . When it is 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.
It is preferably about 1: 2.

The organic acid ester used at this time is
It 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, di-propyl benzoate, butyl benzoate, hexyl benzoate, benzoic acid Cyclopentyl, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate,
Cyclohexyl p-oxybenzoate, salicylsanpendyl, 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,
Examples thereof include benzyl benzoate, methyl naphthoate, ethyl naphthoate and the like. Among these, particularly preferred are benzoic acid, o- or p-threic acid or p.
An alkyl ester of anisic acid, and particularly preferred are methyl ester and ethyl ester thereof.

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 olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all the reactions are carried out in the presence or absence of an inactive hydrocarbon with oxygen and water being substantially cut off. The olefin polymerization conditions are a temperature of 20 to 120 ° C., preferably 50 to 100 ° C., and a pressure of normal pressure to 70 kg / cm.
² , preferably 2 to 60 kg / cm ² . The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system. Of course, by using the catalyst of the present invention, it is possible to carry out the polymerization reaction in two stages or other stages different in polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

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

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

The comonomer content at the time of copolymerization can be arbitrarily selected. The α-olefin content in the polymer is 0 to 40 mol%, preferably 0 to 30 mol%.

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

[Polymer physical property measuring method] Melting point: Using a scanning calorimeter (DSC, manufactured by Seiko Denshi KK), a sample weight of 5 mg was once melted at 180 ° C., then cooled to −40 ° C., and then 10 ° C. The temperature of the endothermic peak top when the temperature was raised at a rate of / min was taken as the melting point. N value: Shimadzu flow tester (CFT-500) is used, various loads are applied to the material at 170 ° C, and the diameter is 2.0 ±
It is extruded from a die having a length of 0.01 mm and a length of 40.0 ± 0.01 mm, and the shear rate gradient with respect to the shear stress is calculated by the following formula to obtain an N value.

[0095]

[Equation 1]

Example 1 (a) Production of solid catalyst component SiO ₂ (Fuji Devison, #
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Hexane was removed by drying under reduced pressure at 0 ° C. (Component [I])

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

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, the whole amount of the solution was added to the three-neck containing the component [I], the mixture was reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours.
Then add 2.0 ml of diethyldiethoxysilane and
The reaction was carried out at 0 ° C for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization A stainless steel autoclave equipped with a stirrer was used as a gas phase polymerization apparatus, and a loop was formed with a blower, a flow rate controller and a dry cyclone, and the autoclave was heated to a temperature by flowing hot water through a jacket. Was adjusted. 250 m of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
g / hr, dimethyldimethoxysilane 0.2 mmol /
hr and triethylaluminum at 50 mmol / h
at a rate of r, and 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, each gas was supplied to adjust the total pressure. Was maintained at 8 kg / cm ² G, gas in the system was circulated by a blower, and continuous polymerization was carried out for 10 hours while intermittently withdrawing the produced polymer. After completion of polymerization
When the inside of the autoclave was inspected, no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 180,000 g copolymer / g
It was highly active with Ti. The ethylene copolymer produced is
Melt flow rate (MFR) 0.76g / 10mi
n, the density is 0.9212 g / cm ³ , and the bulk density is 0.
It was a round granular material having a shape of 49 g / cm ³ and an average particle diameter of 580 μm. The melting point of this copolymer is 120.8 ° C,
The N value was 1.40, indicating a very narrow molecular weight distribution.

Example 2 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 1, 0.18 mmo of diethyldiethoxysilane was used instead of dimethyldimethoxysilane of Example 1.
Gas phase polymerization was carried out in the same manner as in Example 1 except that 1 / hr was used, and the catalyst efficiency was 160,00.
Highly active with 0 g copolymer / g Ti, MFR 0.72 g /
A round granular material having a shape of 10 min, a density of 0.9221 g / cm ³ , a bulk specific gravity of 0.48 g / cm ³ , and an average particle diameter of 530 μm was obtained. The melting point of this copolymer is 12
The molecular weight distribution was extremely narrow at 1.3 ° C. and the n value was 1.42.

Example 3 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 1, methyldimethoxysilane 1.0 mmol / instead of dimethyldimethoxysilane of Example 1 was used.
Gas phase polymerization was performed in the same manner as in Example 1 except that hr was used, and the catalyst efficiency was 190,000 g.
High activity with copolymer / gTi, MFR 0.85g / 10
min, density 0.9210 g / cm ³ , bulk specific gravity 0.4
A round granular material having a shape of 9 g / cm ³ and an average particle size of 590 μm was obtained. The melting point of this copolymer is 121.5.
The N and the N value were 1.42 and the molecular weight was extremely narrow.

Example 4 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 1, bis (dimethylamino) dimethylsilane 0.2 mmol / hr was used in place of dimethyldimethoxysilane of Example 1. Except that the gas phase polymerization was performed in the same manner as in Example 1, except that the catalyst efficiency was as high as 200,000 g copolymer / g Ti and the MFR was high.
0.92g / 10min, density 0.9209g / c
m ³ , bulk specific gravity of 0.49 g / cm ³ , average particle size of 610 μm
Round granules in the form of m were obtained. The melting point of this copolymer was 121.0 ° C. and the n value was 1.41, showing a very narrow molecular weight distribution.

Example 5 (a) Production of solid catalyst component SiO ₂ (Fuji Devison, #
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Hexane was removed by drying under reduced pressure at 0 ° C.

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

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, the whole amount of the solution was added to the three-neck containing the component [I], the mixture was reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours.
Then add 1.4 ml of dimethyldimethoxysilane and
The reaction was carried out at 0 ° C for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r, dimethyldimethoxysilane 0.8 mmol / hr and triethylaluminum were fed at a rate of 50 mmol / hr, and butene-1 // in the autoclave gas phase
Ethylene molar ratio to 0.38 and hydrogen to total pressure of 15
%, While supplying each gas while maintaining the total pressure at 8 kg / cm ² G, the gas in the system is circulated by a blower while continuously discharging the produced polymer for 10 hours of continuous polymerization. went. After the polymerization was completed, the inside of the autoclave was inspected, and it was found that no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 190,000 g copolymer / g
It was extremely highly active with Ti. The ethylene copolymer produced has a melt flow rate (MFR) of 0.81 g / 1.
0min, the density 0.9220g / cm ^3, a bulk density of 0.49 g / cm ^3, was a round particulate matter having the shape of an average particle size of 600 .mu.m. The melting point of this copolymer is 121.
The molecular weight distribution was extremely narrow at 6 ° C and n value of 1.40.

Example 6 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 5, 0.18 mmo of diethyldiethoxysilane was used instead of dimethyldimethoxysilane of Example 1.
Gas phase polymerization was carried out in the same manner as in Example 1 except that 1 / hr was used, and the catalyst efficiency was 160,00.
Highly active with 0 g copolymer / g Ti, MFR 0.95 g /
10min, density 0.9222g / cm ^3, bulk density 0.47 g / cm ^3, a round particulate matter having the shape of an average particle diameter of 550μm was obtained. The melting point of this copolymer is 12
The molecular weight distribution was extremely narrow at 1.8 ° C. and the n value was 1.41.

Example 7 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 5, methyldimethoxysilane 1.0 mmol / instead of dimethyldimethoxysilane of Example 1 was used.
Gas phase polymerization was performed in the same manner as in Example 1 except that hr was used, and the catalyst efficiency was 200,000 g.
High activity with copolymer / gTi, MFR 0.73g / 10
min, density 0.9217 g / cm ³ , bulk specific gravity 0.4
Round granules having a shape of 7 g / cm ³ and an average particle size of 620 μm were obtained. The melting point of this copolymer is 122.0.
The N and the N value were 1.41 and the molecular weight distribution was extremely narrow.

Example 8 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 1, bis (dimethylamino) dimethylsilane 0.2 mmol / hr was used in place of dimethyldimethoxysilane of Example 1. Except that the gas phase polymerization was performed in the same manner as in Example 1 except that the catalyst efficiency was 210,000 g copolymer / g Ti and the activity was high.
1.01g / 10min, density 0.9207g / c
m ³ , bulk specific gravity 0.49 g / cm ³ , average particle size 640 μ
Round granules in the form of m were obtained. The melting point of this copolymer was 121.4 ° C, and the n value was 1.40, indicating a very narrow molecular weight distribution.

Example 9 (a) Production of solid catalyst component SiO ₂ (Fuji Devison, #
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added, and the mixture was reacted again with hexane reflux for 2 hours.
Hexane was removed by vacuum drying at 20 ° C.

10 g of commercially available anhydrous magnesium chloride, 4.2 g of aluminum triethoxide and titanium tetrachloride were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. 7 g was added, and ball milling was performed at room temperature for 16 hours in a nitrogen atmosphere to obtain a reaction product.

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, and the solution was added to a three-necked flask containing the whole amount of the component [I], reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours. Next, 2.0 ml of diethyldiethoxysilane was added and reacted at 90 ° C. for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r, dimethyldimethoxysilane 0.8 mmol / hr and triethylaluminum were fed at a rate of 50 mmol / hr, and butene-1 // in the autoclave gas phase
Ethylene molar ratio to 0.38 and hydrogen to total pressure of 15
%, While supplying each gas while maintaining the total pressure at 8 kg / cm ² G, the gas in the system is circulated by a blower while continuously discharging the produced polymer for 10 hours of continuous polymerization. went. After the polymerization was completed, the inside of the autoclave was inspected, and it was found that no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 220,000 g copolymer / g
It was extremely highly active with Ti. The produced ethylene copolymer has a melt flow rate (MFR) of 1.13 g / 1.
0min, the density 0.9204g / cm ^3, a bulk density of 0.49 g / cm ^3, was a round particulate matter having the shape of an average particle diameter of 660μm. The melting point of this copolymer is 121.
The molecular weight distribution was extremely narrow at 8 ° C. and the n value was 1.41.

Example 10 (a) Preparation of solid catalyst component SiO ₂ (Fuji Davison, #
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Hexane was removed by drying under reduced pressure at 0 ° C.

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

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, the whole amount of the solution was added to the three-neck containing the component [I], the mixture was reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours.
Next, 1.0 ml of bis (dimethylamino) dimethylsilane
Was added and reacted at 90 ° C. for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r, dimethyldimethoxysilane 0.8 mmol / hr and triethylaluminum were fed at a rate of 50 mmol / hr, and butene-1 // in the autoclave gas phase
Ethylene molar ratio to 0.38 and hydrogen to total pressure of 15
%, While supplying each gas while maintaining the total pressure at 8 kg / cm ² G, the gas in the system is circulated by a blower while continuously discharging the produced polymer for 10 hours of continuous polymerization. went. After the polymerization was completed, the inside of the autoclave was inspected, and it was found that no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 190,000 g copolymer / g
It was extremely highly active with Ti. The produced ethylene copolymer has a melt flow rate (MFR) of 1.20 g / 1.
0min, the density 0.9211g / cm ^3, a bulk density of 0.47 g / cm ^3, was a round particulate matter having the shape of an average particle size of 600 .mu.m. The melting point of this copolymer is 121.
The molecular weight distribution was extremely narrow at 8 ° C. and the n value was 1.41.

Example 11 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 10, bis (dimethylamino) dimethylsilane 0.2 mmol / hr was used in place of dimethyldimethoxysilane of Example 10. Except that the gas phase polymerization was performed in the same manner as in Example 10, except that the catalyst efficiency was 180,000 g copolymer / g Ti, high activity, and M
FR 1.16g / 10min, density 0.9209g / c
m ³ , bulk specific gravity 0.49 g / cm ³ , average particle size 590 μ
Round granules in the form of m were obtained. The melting point of this copolymer was 121.8 ° C., and the n value was 1.40, indicating a very narrow molecular weight distribution.

Example 12 (a) Production of solid catalyst component SiO ₂ (Fuji Devison, #
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added, and the mixture was reacted again with hexane reflux for 2 hours.
Hexane was removed by vacuum drying at 20 ° C. (Component [I])

10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide and titanium tetrachloride were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. 7 g was added, and ball milling was performed at room temperature for 16 hours in a nitrogen atmosphere to obtain a reaction product.

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, and the solution was added to a three-necked flask containing the whole amount of the component [I], reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours. Next, bis (dimethylamino) dimethylsilane 1.
2 ml was added and reacted at 90 ° C. for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r, dimethyldimethoxysilane 1.0 mmol / hr and triethylaluminum were fed at a rate of 50 mmo1 / hr, and butene-1 // in the autoclave gas phase
Ethylene molar ratio to 0.38 and hydrogen to total pressure of 15
%, While supplying each gas while maintaining the total pressure at 8 kg / cm ² G, the gas in the system is circulated by a blower while continuously discharging the produced polymer for 10 hours of continuous polymerization. went. After the polymerization was completed, the inside of the autoclave was inspected, and it was found that no polymer was attached to the inner wall and the stirrer.

The catalyst efficiency is 210,000 g copolymer / g
It was extremely highly active with Ti. The produced ethylene copolymer has a melt flow rate (MFR) of 0.88 g / 1.
It was a round granular material having a shape of 0 min, a density of 0.9198 g / cm ³ , a bulk density of 0.48 g / cm ³ , and an average particle size of 620 μm. The melting point of this copolymer is 122.
The molecular weight distribution was extremely narrow at 1 ° C. and the n value was 1.42.

Example 13 In carrying out gas phase polymerization using the solid catalyst component prepared in Example 12, 0.2 mmol / hr of bis (dimethylamino) dimethylsilane was used instead of methyldimethoxysilane of Example 12. Except that the gas phase polymerization was performed in the same manner as in Example 12, except that the catalyst efficiency was 230,000 g copolymer / gTi and the activity was MF.
R0.89g / 10min, density 0.9211g / cm
³ , bulk specific gravity 0.49 g / cm ³ , average particle size 680 μm
Round granules of the form were obtained. The melting point of this copolymer was 121.9 ° C., and the n value was 1.40, indicating a very narrow molecular weight distribution.

Example 14 A solid catalyst component was synthesized in the same manner as in Example 1 except that Al ₂ O ₃ was used instead of SiO ₂ in Example 1.

Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, and the catalyst efficiency was 140,000.
It was highly active with g copolymer / gTi. The ethylene copolymer produced has a melt flow rate (MFR) of 0.59.
g / 10 min, density 0.9224 g / cm ³ ,
It was a round granular material having a bulk density of 0.46 g / cm ³ and an average particle size of 520 μm. The melting point of this copolymer was 122.5 ° C, and the n value was 1.41, showing a very narrow molecular weight distribution.

[0131] Example 15 _SiO 2 -Al ₂ instead of SiO ₂ in Example 1
A solid catalyst component was synthesized in the same manner as in Example 1 except that O ₃ was used.

Polymerization was carried out in the same manner as in Example 1 using the above solid catalyst component, and the catalyst efficiency was 150,000.
It was highly active with g copolymer / gTi. The ethylene copolymer produced has a melt flow rate (MFR) of 0.71.
g / 10 min, density 0.9229 g / cm ³ ,
It was a round granular material having a bulk density of 0.47 g / cm ³ and an average particle size of 520 μm. The melting point of this copolymer was 122.7 ° C., and the n value was 1.41, showing a very narrow molecular weight distribution.

Comparative Example 1 (a) Manufacture of solid catalyst component SiO ₂ (Fuji Davison, # #) burned at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Hexane was removed by drying under reduced pressure at 0 ° C.

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

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, the whole amount of the solution was added to the three-neck containing the component [I], the mixture was reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours.
Then add 1.4 ml of dimethyldimethoxysilane and
The reaction was carried out at 0 ° C for 3 hours to obtain a solid catalyst component.

(B) Gas phase polymerization Using the same gas phase polymerization apparatus as in Example 1, 250 mg / h of the above solid catalyst component was placed in an autoclave adjusted to 80 ° C.
r and triethylaluminum at 50 mmol / hr
Of the butene in the gas phase of the autoclave.
1 / Ethylene molar ratio was set to 0.35, and each gas was supplied while adjusting 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 the produced polymer was intermittently withdrawn to carry out continuous polymerization for 10 hours.

The catalyst efficiency is 240,000 g copolymer / g
The ethylene copolymer which is highly active with Ti and has a melt flow rate (MFR) of 0.95 g / 10 min,
The density is 0.9196 g / cm ³ , and the bulk density is 0.47.
Although it was a round granule having a shape of g / cm ³ and an average particle diameter of 600 μm, the N value was 1.45, and the molecular weight distribution was wider than that of the examples of the present invention. The melting point was 122.1 ° C.

Comparative Example 2 (a) Manufacture of solid catalyst component SiO ₂ (Fuji Davison, # #) burned at 600 ° C. in a 500 ml three-necked flask equipped with a stirrer and a reflux condenser.
955) 50 g, and 160 ml of dehydrated hexane and 3.3 ml of titanium tetrachloride are added, and hexane refluxed under 3
Reacted for hours. After cooling, 45 ml of a 1 mmol / cc hexane solution of diethylaluminum chloride was added and reacted again with hexane reflux for 2 hours.
Hexane was removed by drying under reduced pressure at 0 ° C.

[0139] Commercially available anhydrous magnesium chloride (10 g) and aluminum triethoxide (4.2 g) were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch and nitrogen atmosphere. Ball milling was performed for 16 hours at room temperature to obtain a reaction product.

5.4 g of the reaction product was added to dehydrated ethanol 1
It was dissolved in 60 ml, the whole amount of the solution was added to the three-neck containing the component [I], the mixture was reacted under ethanol reflux for 3 hours, and then dried under reduced pressure at 150 ° C. for 6 hours.
Next, 1.0 ml of bis (dimethylamino) dimethylsilane
Was added and reacted at 90 ° C. for 3 hours to obtain a solid catalyst component.

(B) Gas Phase Polymerization Polymerization was carried out using the above solid catalyst component under the same conditions as in Comparative Example 1. The catalyst efficiency was as high as 230,000 g copolymer / gTi, and the produced ethylene was produced. The copolymer has a melt flow rate (MFR) of 1.02 g / 10 m.
in, the density 0.9199g / cm ^3, compared bulk density 0.47 g / cm ^3, was the round granulate of the shape of an average particle diameter of 690μm, N value from the embodiment of the present invention with 1.44 The molecular weight distribution was wide. The melting point was 122.1 ° C.

[0142]

EFFECT OF THE INVENTION The olefin homopolymer or copolymer obtained by using the solid catalyst component and the organometallic compound as a catalyst of the present invention has a remarkably high bulk specific gravity, a relatively large average particle diameter, and a narrow particle diameter distribution. Because there are few fine powder particles,
Stable operation is possible with less polymer adhering to the reactor wall during polymerization, moreover, it is possible to prevent the generation of dust during molding and improve the efficiency during molding, as well as the pelletizing process. Can also be omitted.

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

[Brief description of drawings]

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

Claims (2)

[Claims] 1. A solid catalyst component obtained by first reacting a reaction product of the following (1) with a reaction product of the above (2) and then reacting the reaction product of the above reaction product with the reaction product of the above (3); (1) a) silicon oxide and / or aluminum oxide and b) a reaction product obtained by reacting a titanium compound or a titanium compound and a vanadium compound with c) an organoaluminum compound. , (2) a) magnesium halide and b) general formula Me (OR) _n X _z-n (where Me is an element of Group I to IV of the periodic table, and z is an element M).
a valence of e, n is 0 <n ≦ z, X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, and a reaction product obtained by reacting the compound and 3) Silicon compounds having at least one Si-O-C bond and / or at least one Si-N-C bond, [II] at least one Si-O-C bond and / or at least one Si-N-. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin with a catalyst system comprising a combination of a silicon compound having a C bond and [III] an organometallic compound. 2. [I] A solid catalyst component obtained by first reacting the reaction product of the following (1) with the reaction product of (2) and reacting the reaction product with the reaction product of (3); (1) a) silicon oxide and / or aluminum oxide and b) a reaction product obtained by reacting a titanium compound or a titanium compound and a vanadium compound with a c) an organoaluminum compound. , (2) a) magnesium halide and b) general formula Me (OR) _n X _z-n (where Me is an element of Group I to IV of the periodic table, and z is an element M).
the valence of e, n is 0 <n ≦ z, X is a halogen atom, R is a hydrocarbon residue having 1 to 20 carbon atoms, and c) a titanium compound or a titanium compound and a vanadium compound And a reaction product obtained by reacting (3) a silicon compound having at least one Si—O—C bond and / or at least one Si—N—C bond, [II] at least one Si—O—C A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin with a catalyst system comprising a bond and / or a silicon compound having at least one Si—N—C bond and [III] an organometallic compound.