JP2001247617A - Process for polymerizing alpha-olefin and alpha-olefin polymer produced thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an α-olefin polymer having high stereoregularity and a broad molecular weight distribution in high polymerization activity. SOLUTION: There is provided a process for polymerizing an α-olefin comprising polymerizing or copolymerizing an α-olefin in the presence of a catalyst comprising (A) a solid catalyst component essentially consisting of magnesium, titanium, a halogen, and an electron donor; (B) an organoaluminum compound component; (C) di(cyclopentyl) dimethoxysilane, and (D) a specified polycyclic aminosilane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel catalyst component comprising a combination of an organosilicon compound having a specific structure and a highly active, highly stereoregular,
And a homopolymer of α-olefin having a wide molecular weight distribution,
Alternatively, the present invention relates to a method for producing a copolymer with another α-olefin.

[0002]

2. Description of the Related Art In recent years, in order to polymerize an α-olefin, magnesium, titanium, a halogen element and an electron donor are indispensable for a solid catalyst component, an organometallic compound of a group 1 to 3 metal of the periodic table, and an electron. High activity supported catalyst systems comprising a donor are disclosed in JP-A-57-63310 and JP-A-5-63310.
Many proposals have been made in JP-A-8-83016, JP-A-59-58010, JP-A-60-44507. Furthermore, JP-A-62-1705, JP-A-63-259807, and JP-A-2-84404.
JP, JP-A-4-202505, JP-A-4-3
No. 70103 discloses a polymerization catalyst characterized by using a specific organosilicon compound as an electron donor.

[0003] However, the propylene polymer obtained using the above-mentioned supported catalyst system usually has a narrow molecular weight distribution and a small viscoelasticity when the polymer is melted. May be a problem. To solve this problem, JP-A-63-245408, JP-A-2-232207, and JP-A-4-370.
No. 103 discloses a method of expanding the molecular weight distribution by polymerization using a plurality of polymerization vessels or multi-stage polymerization. However, such a method requires a complicated operation and has to reduce the production speed industrially, which is not preferable in view of cost. Furthermore, in order to produce a propylene polymer having a low molecular weight and a wide molecular weight distribution in a plurality of polymerization vessels, one of the polymerization vessels must produce an excess of a chain transfer agent such as hydrogen to produce a low molecular weight polymer. Must
In a polymerization reactor with a pressure limit, the polymerization temperature must be lowered,
There is a problem that adversely affects the production speed.

[0004] Also, Japanese Patent Application Laid-Open Nos. 8-1220021, 8-143621 and 8-231636.
In Japanese Patent Application Laid-Open Publication No. H11-163, a method using a cyclic aminosilane compound is disclosed, but there is a problem that the molecular weight distribution is not necessarily wide in these specifically described compounds.

Japanese Patent Application Laid-Open Nos. 6-25336, 7-90012, and 7-97411 disclose nitrogen in which an arbitrary carbon atom in a heterocyclic ring is directly bonded to a silicon atom. A method using an atom-containing heterocyclic-substituted organosilicon compound is disclosed, but the molecular weight distribution is not described. In addition, JP-A-3-74393 and JP-A-7-173212 disclose a method using a monocyclic amino group-containing organosilicon compound, but do not disclose the molecular weight distribution.

On the other hand, a propylene polymer having a wide molecular weight distribution and a stereoregularity can be obtained by previously producing a high stereoregular low molecular weight propylene polymer and a high crystalline high molecular weight propylene polymer by a conventional method. Then, a method of melting and mixing them at a desired ratio can be considered. However, even in this case, if it is intended to produce a propylene polymer having a relatively low molecular weight and a wide molecular weight distribution, it is extremely difficult to uniformly melt-mix the low molecular weight propylene polymer and the high molecular weight propylene polymer. This causes problems such as gel formation.

[0007] EP-A-841348 (Japanese Unexamined Patent Application Publication No.
218926), by using a method using a specific polycyclic amino group-containing organosilicon compound, high stereoregularity,
In addition, a method for obtaining an α-olefin polymer having a wide molecular weight distribution is disclosed, but there is a problem that the polymerization activity is lower than when a conventional organosilicon compound is used.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a high activity, a high stereoregularity, and
An object is to provide an α-olefin polymer having a wide molecular weight distribution.

[0009]

According to the present invention, there are provided [A] a catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] di (cyclopentyl) dimethoxy. Silane

[D] The organosilicon compound component represented by the general formula (1)

[0011]

Embedded image (However, in (1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.) The present invention relates to a method for polymerizing an α-olefin, which comprises polymerizing or copolymerizing an α-olefin in the presence of a catalyst.

Further, the present invention relates to an α-olefin polymer produced by the above polymerization method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a solid catalyst component essentially containing magnesium, titanium, a halogen element, and an electron donor is used as the component [A]. The method for producing the solid catalyst component of the component [A] is not particularly limited, and examples thereof include JP-A-54-94590, JP-A-5-55405, JP-A-56-45909, and JP-A-56-45909. -16
3102, JP-A-57-63310, JP-A-57-115408, and JP-A-58-83006
JP-A-58-83016 and JP-A-58-83016
138707, JP-A-59-149905, JP-A-60-23404, JP-A-60-32
805, JP-A-61-18330, JP-A-61-55104, JP-A-2-77413, and JP-A-2-117905 can be employed.

As a typical production method of the component [A],
(1) A method of co-milling a magnesium compound such as magnesium chloride, an electron donor, and a titanium halide compound such as titanium tetrachloride, and (2) dissolving the magnesium compound and the electron donor in a solvent, and halogenating the solution. A method of adding a titanium compound to precipitate a catalyst solid is exemplified.

As the component [A], JP-A-60-152
The catalyst solid components described in JP-A-511-511, JP-A-61-31402 and JP-A-62-81405 are particularly preferred for achieving the effects of the present invention. According to these production methods, a solid is deposited by reacting an aluminum halide with a silicon compound and further reacting a Grignard compound. As the aluminum halide that can be used in the above reaction, anhydrous aluminum halide is preferable, but it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water is also used. Can be. Specific examples of aluminum halide include aluminum trichloride, aluminum tribromide, and aluminum triiodide, and aluminum trichloride is particularly preferable.

Specific examples of the silicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane, and dimethyldimethoxysilane. Ethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane,
Trimethylmonoethoxysilane and trimethylmonobutoxysilane can be exemplified. Particularly, methylphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane are preferable.

The amount of the compound used in the reaction between the aluminum halide and the silicon compound is determined by the element ratio (Al / Si)
Is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3, and it is preferable to use an inert solvent such as hexane or toluene for the reaction. The reaction temperature is usually 1
The reaction temperature is 0 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is usually 0.2 to 5 hours, preferably 0.5 to 3 hours.

Specific examples of the magnesium compound used in the above reaction include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, propyl magnesium bromide, butyl magnesium bromide, ethyl Magnesium iodide. As the solvent for the magnesium compound, for example, aliphatic ethers such as diethyl ether, dibutyl ether, diisopropyl ether and diisoamyl ether, and aliphatic cyclic ethers such as tetrahydrofuran can be used.

The amount of the magnesium compound to be used is usually 0.5 to 3, preferably 1, in terms of an element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound. 5-
The range is 2.3. The reaction temperature is usually -50 to 100
℃, preferably -20 to 50 ℃, the reaction time is usually 0.2
-5 hours, preferably 0.5-3 hours.

The white solid obtained in the reaction of the aluminum halide with the silicon compound and subsequently with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. As a method of contact treatment,
(1) a method in which a solid is treated with a titanium halide compound, then treated with an electron donor, and then treated again with a titanium halide compound; and (2) the solid is treated in the coexistence of a titanium halide compound and an electron donor. After that, a conventionally well-known method such as a method of treating with a titanium halide compound can be employed.

For example, the above-mentioned solid is dispersed in an inert solvent and an electron donor and / or a titanium halide compound is dissolved therein, or an electron donor and / or a liquid halide is used without using an inert solvent. Disperse the solid in the titanium compound. In this case, the contact treatment between the solid and the electron donor or / and the titanium halide compound is performed under stirring.
The temperature is usually 50 to 150 ° C., and the contact time is not particularly limited, but can be usually 0.2 to 5 hours. Further, this contact processing can be performed a plurality of times.

Specific examples of titanium halide compounds usable for the contact treatment include tetrachlorotitanium, tetrabromotitanium, trichloromonobutoxytitanium, tribromomonoethoxytitanium, trichloromonoisopropoxytitanium, dichlorodiethoxytitanium, dichlorodiethoxytitanium and the like. Butoxytitanium, monochlorotriethoxytitanium and monochlorotributoxytitanium can be mentioned. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferred.

The electron donor used in the contact treatment is a Lewis basic compound, preferably an aromatic diester, particularly preferably an orthophthalic diester. Specific examples of the orthophthalic diester include diethyl orthophthalate, di-n-butyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, di-n-hexyl orthophthalate, di-2-ethylhexyl orthophthalate, and di-ethylhexyl orthophthalate.
n-Heptyl, di-n-octyl orthophthalate and the like. Further, as an electron donor, JP-A-3-70
No. 6, No. 3-62805, No. 4-27070
Compounds having two or more ether groups, such as those described in JP-A Nos. 5 and 6-25332, can also be preferably used.

After the above-mentioned contact treatment, the treated solid is generally separated from the treated mixture and washed sufficiently with an inert solvent to obtain a solid as the catalyst solid component [A] of the present invention. Can be used as

As the organoaluminum compound component [B] of the present invention, alkylaluminum, alkylaluminum halide and the like can be used. Alkylaluminum is preferable, and trialkylaluminum is particularly preferable. , Triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like. Any of the above-mentioned organoaluminum compounds can be used as a mixture. Further, a polyaluminoxane obtained by a reaction between an alkyl aluminum and water can be used in the same manner.

The amount of the organoaluminum compound component [B] used as the polymerization catalyst for the α-olefin is represented by an element molar ratio (Al / Ti) of the solid catalyst component [A] to titanium.
It is 0.1 to 1000, preferably 100 to 600.

In the present invention, in addition to the above [A] and [B], di (cyclopentyl) dimethoxysilane is used as the component [C], and the general formula is used as the component [D].
Organosilicon compound component represented by (1)

[0028]

Embedded image (However, in (1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.) The α-olefin is polymerized or copolymerized with a catalyst comprising

R ^{1 in the} organosilicon compound component represented by the general formula (1) is a hydrocarbon group having 1 to 8 carbon atoms, such as an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. Can be

Specific examples include a methyl group, an ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, i
Examples thereof include a so-butyl group, a ter-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group. Particularly preferred is a methyl group.

R ² N is a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom. The polycyclic amino group may be a saturated polycyclic amino group or a polycyclic amino compound in which a part of the ring is unsaturated.

The nitrogen atom of the polycyclic amino group is directly bonded to the silicon atom of the organosilicon compound. That is, the hydrogen atom of the secondary amine R ² NH is removed and Si and N are chemically bonded. In the general formula (2), the two R ² N groups may be the same or different.

As a specific example of R ² NH, as shown by the following chemical structural formula,

[0034]

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Perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroacridine,
Perhydrophenanthridine, perhydrobenzo (g)
Quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline, par- Amine compounds such as hydroaceisoquinoline and perhydroiminostilbene, and further include amine compounds in which a part of hydrogen atoms other than the nitrogen atom in the amine compound is substituted with an alkyl group, a phenyl group, or a cycloalkyl group. it can.

R ² NH is represented by the following chemical structural formula:

[0037]

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1,2,3,4-tetrahydroquinoline,
Polycyclic amino groups such as 1,2,3,4-tetrahydroisoquinoline in which a part of the ring is unsaturated, and part of the hydrogen atoms other than the nitrogen atom are substituted by an alkyl group, a phenyl group or a cycloalkyl group Amine compounds.

Particularly preferred R ³ NH is perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline And their derivatives.

As the organosilicon compound represented by the general formula (1), a perhydroquinolino compound represented by the general formula (2), a perhydroisoquinolino compound represented by the general formula (3), (Perhydroquinolino) represented by the formula (4) (Perhydroisoquinoli compound, 1,2,3,4-tetrahydroquinolino compound represented by the general formula (5),
1,2,3,4-tetrahydroisoquinolino compound represented by the general formula (6), and (1,2,3,4)
-Tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compound and the like.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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R ³ represents a substituent on the saturated ring of R ² N, and is hydrogen or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred as R ³ are hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, ter-butyl group, sec-butyl group and the like. The number of hydrocarbon substituents on the saturated ring of R ² N may be one or more.

The compound represented by the general formula (2) includes
Bis (perhydroquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (2-methylperhydroquinolino) dimethoxysilane, bis (3-methylperhydroquinolino) dimethoxysilane, bis (4-methylperhydroquinolino) dimethoxysilane, bis (5-methylperhydroquinolino) dimethoxysilane,
(Hydroquinolino) dimethoxysilane, bis (6-methylperhydroquinolino) dimethoxysilane, bis (7-methylperhydroquinolino) dimethoxysilane, bis (8
-Methylper-hydroquinolino) dimethoxysilane, bis (9-methylper-hydroquinolino) dimethoxysilane,
Examples include bis (methyl-substituted per-hydroquinolino) dimethoxysilane such as bis (10-methylper-hydroquinolino) dimethoxysilane.

Further, bis (2,3-dimethylperhydroquinolino) dimethoxysilane, bis (2,4-dimethylperhydroquinolino) dimethoxysilane, bis (2,5
-Dimethylperhydroquinolino) dimethoxysilane, bis (2,6-dimethylperhydroquinolino) dimethoxysilane, bis (2,7-dimethylperhydroquinolino)
Dimethoxysilane, bis (2,8-dimethylperhydroquinolino) dimethoxysilane, bis (2,9-dimethylperhydroquinolino) dimethoxysilane, bis (2,1
0-dimethylper-hydronorino) dimethoxysilane,
Bis (3,4-dimethylpa-hydroquinolino) dimethoxysilane, bis (3,5-dimethylpa-hydroquinolino) dimethoxysilane, bis (3,6-dimethylpa-hydroquinolino) dimethoxysilanebis (3,7-dimethylpa-hydroquinolino) dimethoxysilane , Screws (3,
8-dimethylper-hydroquinolino) dimethoxysilane,
Bis (3,9-dimethylper-hydroquinolino) dimethoxysilane, bis (3,10-dimethylper-hydroquinolino) dimethoxysilane, bis (4,5-dimethylper-hydroquinolino) dimethoxysilane, bis (4,6-dimethylper-hydroquinolino) dimethoxy Silane, bis (4,7-dimethylper-hydroquinolino) dimethoxysilane, bis (4,8-dimethylper-hydroquinolino) dimethoxysilane, bis (4.9-dimethylper-hydroquinolino) dimethoxysilane, bis (4,10-dimethylper-hydroquinolino) ) Dimethoxysilane, bis (5,6
-Dimethylperhydroquinolino) dimethoxysilane, bis (5.7-dimethylperhydroquinolino) dimethoxysilane, bis (5,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (5,9-dimethylper-hydroquinolino) dimethoxysilane, bis (5,10-dimethylper-hydroquinolino) dimethoxysilane, bis (6
7-dimethylper-hydroquinolino) dimethoxysilane,
Bis (6,8-dimethylper-hydroquinolino) dimethoxysilane, bis (6,9-dimethylper-hydroquinolino) dimethoxysilane, bis (6,10-dimethylper-hydroquinolino) dimethoxysilane, bis (7,8-
Dimethyl per-hydroquinolino) dimethoxysilane, bis (7,9-dimethyl per-hydroquinolino) dimethoxysilane, bis (7,10-dimethyl per-hydroquinolino)
Dimethoxysilane, bis (8,9-dimethylperhydroquinolino) dimethoxysilane, bis (8,10-dimethylperhydroquinolino) dimethoxysilane, bis (9,
Bis (dimethyl-substituted per-hydroquinolino) dimethoxysilane such as 10-dimethylper-hydroquinolino) dimethoxysilane.

In addition, bis (2,3,4-trimethyl
Hydroquinolino) dimethoxysilane, bis (3,4,5)
-Trimethylper-hydroquinolino) dimethoxysilane,
Bis (4,5,6-trimethylperhydroquinolino) dimethoxysilane, bis (5,6,7-trimethylperhydroquinolino) dimethoxysilane, bis (6,7,8-
Bis (trimethyl-substituted perhydroquinolino) dimethoxy such as trimethylper-hydroquinolino) dimethoxysilane, bis (7,8,9-trimethylper-hydroquinolino) dimethoxysilane, bis (8,9,10-trimethylpa-hydroquinolino) dimethoxysilane A silane compound is exemplified.

Further, (per-hydroquinolino) (2-methylper-hydroquinolino) dimethoxysilane, (per-hydroquinolino) (3-methylpa-hydroquinolino) dimethoxysilane, (per-hydroquinolino) (4-methylpar-
(Hydroquinolino) dimethoxysilane, (per-hydroquinolino) (5-methylper-hydroquinolino) dimethoxysilane, (per-hydroquinolino) (6-methylpa-hydroquinolino) dimethoxysilane, (per-hydroquinolino)
(7-methylperhydroquinolino) dimethoxysilane,
(Perhydroquinolino) (8-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (9-
Methyl perhydroquinolino) dimethoxysilane,
Compounds such as (hydroquinolino) (10-methylper-hydroquinolino) dimethoxysilane.

Of the above compounds, bis (perhydroquinolino) dimethoxysilane is particularly preferred.

The compound represented by the general formula (3) includes
Bis (perhydroisoquinolino) dimethoxysilane; and the like.

Further, bis (1-methylperhydroisoquinolino) dimethoxysilane, bis (3-methylperhydroisoquinolino) dimethoxysilane, bis (4-methylperhydroisoquinolino) dimethoxysilane, bis (5
-Methylper-hydroisoquinolino) dimethoxysilane,
Bis (6-methylperhydroisoquinolino) dimethoxysilane, bis (7-methylperhydroisoquinolino) dimethoxysilane, bis (8-methylperhydroisoquinolino) dimethoxysilane, bis (9-methylperhydroisoquinolino) dimethoxysilane Bis (methyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as quinolino) dimethoxysilane and bis (10-methylper-hydroisoquinolino) dimethoxysilane are exemplified.

Further, bis (1,3-dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,4-dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,5-dimethylper-hydroisoquinolino) Dimethoxysilane, bis (1,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,7-dimethylpar-
(Hydroisoquinolino) dimethoxysilane, bis (1,8
-Dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,9-dimethylper-hydroisoquinolino)
Dimethoxysilane, bis (1,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,5-dimethylperhydroisoquinolino) dimethoxysilane , Bis (3,6-dimethylper-hydroisoquinolino) dimethoxysilane, bis (3,7-dimethylper-hydroisoquinolino) dimethoxysilane, bis (3
8-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,9-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (3,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,5-
Dimethyl per-hydroisoquinolino) dimethoxysilane,
Bis (4,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,8-dimethylperhydroisoquinolino) dimethoxysilane, bis ( 4,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,6-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5
7-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,8-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (5,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (6,7-dimethylper-hydroisoquinolino) dimethoxysilane , Bis (6,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (6,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (6
10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,10
-Dimethylper-hydroisoquinolino) dimethoxysilane, bis (8,9-dimethylper-hydroisoquinolino)
Dimethoxysilane, bis (8,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (9,10-
Bis (dimethyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as dimethylper-hydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4-trimethylpar-
Hydroisoquinolino) dimethoxysilane, bis (3,
4,5-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (4,5,6-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (5,6,7-trimethylpa-hydroisoquinolino) Dimethoxysilane,
Bis (6,7,8-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (7,8,9-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (8,9,10-trimethylpa-hydro) Bis (trimethyl-substituted phenols such as isoquinolino) dimethoxysilane
Hydroisoquinolino) dimethoxysilane compounds.

Further, (perhydroisoquinolino) (2-
Methyl per-hydroisoquinolino) dimethoxysilane,
(Per-hydroisoquinolino) (3-methylper-hydroisoquinolino) dimethoxysilane, (per-hydroisoquinolino) (4-methylper-hydroisoquinolino) dimethoxysilane, (per-hydroisoquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (6-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino)
(7-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (8-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (9-methylperhydroisoquino) Compounds such as (lino) dimethoxysilane and (per-hydroisoquinolino) (10-methylper-hydroisoquinolino) dimethoxysilane.

Of the above compounds, bis (perhydroisoquinolino) dimethoxysilane is particularly preferred.

As the compound represented by the general formula (4),
(Per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (per-hydroquinolino) (1-methylper-hydroisoquinolino) dimethoxysilane, (per-hydroquinolino) (3-methylper-hydroisoquinolino)
Dimethoxysilane, (perhydroquinolino) (4-methylperhydroisoquinolino) dimethoxysilane,
Hydroquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (6-
Methyl per-hydroisoquinolino) dimethoxysilane,
(Perhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino)
(8-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (9-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (10-methylperhydroisoquinolino) dimethoxysilane, ( 2-methylperhydroquinolino (perhydroisoquinolino) dimethoxysilane, (3-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (4-methylperhydroquinolino) (part
(Hydroisoquinolino) dimethoxysilane, (5-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (6-methylpa-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) ) (Perhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinolino)
(Perhydroisoquinolino) dimethoxysilane, (9-
Methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (10-methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane,
(2-methylpa-hydroquinolino) (1-methylpa-hydroisoquinolino) dimethoxysilane, (3-methylpa-hydroquinolino) (3-methylpa-hydroisoquinolino) dimethoxysilane, (4-methylpa-hydroquinolino) (4- (5-methylperhydroisoquinolino) dimethoxysilane, (5-methylperhydroisoquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (6-
Methyl per-hydroquinolino (6-methyl per-hydroisoquinolino) dimethoxysilane, (7-methyl per-hydroquinolino) (7-methyl per-hydroisoquinolino) dimethoxysilane, (8-methyl per-hydroquinolino)
(8-methylpa-hydroisoquinolino) dimethoxysilane, (9-methylpa-hydroquinolino) (9-methylpa-hydroisoquinolino) dimethoxysilane, (10-methylpa-hydroquinolino) (10-methylpa-hydroisoquinolino) Examples include compounds such as dimethoxysilane.

Of the above compounds, (per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane is particularly preferred.

As the compound represented by the general formula (5),
Bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (2-methyl-1,2,3,4
-Tetrahydroquinolino) dimethoxysilane, bis (3
-Methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4-methyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (6-
Methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (7-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (8-methyl-1,2,3, Bis (methyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane such as 4-tetrahydroquinolino) dimethoxysilane and bis (9-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane Compounds.

Further, bis (2,3-dimethyl-1,2,2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (2,4-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,6-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (2,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,8
-Dimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (2,9-dimethyl-1,2,2
3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,6-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (3,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,8
-Dimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (3,9-dimethyl-1,2,2
3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,7-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (4,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,9
-Dimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (6,7-dimethyl-1,2,2
3,4-tetrahydroquinolino) dimethoxysilane, bis (6,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,9-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (7,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (7,9
-Dimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (8,9-dimethyl-1,2,2
Bis (dimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as 3,4-tetrahydroquinolino) dimethoxysilane;

Further, bis (2,3,4-trimethyl-
1,2,3,4-tetrahydroquinolino) dimethoxysilabis (2,3,6-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2
3,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2 3,9-trimethyl-1,2,2
3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,7
-Trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,9 -Trimethyl-1,2,3,
4-tetrahydroquinolino) dimethoxysilane, bis (4,6,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6,8-
Trimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (4,6,9-trimethyl-
1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,7,8-trimethyl-1,2,3,4
-Tetrahydroquinolino) dimethoxysilane, bis (6,7,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (7,8,9-
Trimethyl-1,2,3,4-tetrahydroquinolino)
Bis (trimethyl-substituted-1, such as dimethoxysilane,
2,3,4-tetrahydroquinolino) dimethoxysilane compound.

Further, bis (2,3,4,6-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,7-tetramethyl-1,
2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,8-tetramethyl-1,2,2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,9-tetramethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (3,
4,6,7-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,
8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis ( 4,6,7,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6,7,9-tetramethyl-1,
2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,7,8,9-tetramethyl-1,2,2
Compounds such as (tetramethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane such as 3,4-tetrahydroquinolino) dimethoxysilane are exemplified.

Among the above compounds, bis (1,2,2
3,4-Tetrahydroquinolino) dimethoxysilane dimethoxysilane is particularly preferred.

Further, bis (perhydroindolino) dimethoxysilane, bis (perhydroindisoindolino)
Dimethoxysilane and the like can also be preferably used.

Specific examples of the organosilicon compound represented by the general formula (1) include compounds represented by the following chemical structural formulas.

[0070]

Embedded image

[0071]

Embedded image

The organosilicon compound having two polycyclic amino groups includes a geometrical isomer,
That is, since there are cis-form and trans-form,
(Trans-polycyclic amino) (trans-polycyclic amino) dialkoxysila (cis-polycyclic amino) (cis-
There are polycyclic amino) dialkoxysilanes, (trans-polycyclic amino) (cis-polycyclic amino) dialkoxysilanes.

As specific examples, bis (trans-per-hydroquinolino) dimethoxysilane, bis (cis-per-hydroquinolino) dimethoxysilane, bis (trans-per-
Hydroisoquinolino) dimethoxysilane, bis (cis-
(Perhydroisoquinolino) dimethoxysilane and the like. These isomers may be used alone or as a mixture of isomers as the component [D] of the present invention.

The organosilicon compound component [D] represented by the general formula (1) is synthesized, for example, by reacting tetramethoxysilane or dichlorodimethoxysilane with two equivalents of a magnesium or lithium salt of an HNR secondary amine. can do.

The component [C] and the component [D] may be used by mixing them in advance, or may be used by adding each alone to the polymerization system. The mixture molar ratio ([C] /
[D]) is from 0.01 to 1, preferably from 0.02 to
1, particularly preferably 0.05 to 0.5.

The polymerization method in the present invention includes a slurry polymerization method using a non-polar solvent such as propane, butane, pentane, hexane, heptane and octane, and a monomer polymerization method.
A gas phase polymerization method in which the polymer is brought into contact with a catalyst in a gaseous state to carry out polymerization, or a bulk polymerization method in which a monomer in a liquefied state is polymerized in a solvent as a solvent can be adopted. In the above polymerization method, either continuous polymerization or batch polymerization may be performed.

The polymerization pressure is 0.1 to 20 MPa, preferably 1 to 6 MPa, and the polymerization temperature is 10 to 150 ° C., preferably 30 to 100 ° C., particularly preferably 60 to 90 ° C.
The polymerization time is usually 0.1 to 10 hours, preferably 0.5 to
The range is 7 hours.

In the present invention, ethylene or α-
It is preferable that the olefin is preliminarily polymerized according to the above-mentioned various polymerization methods, and then the main polymerization of the α-olefin is performed.
The effects of the prepolymerization include improvement in polymerization activity, improvement in stereoregularity of the polymer, and stabilization of the particle shape of the polymer. As a method of the prepolymerization, the catalyst solid component [A] is previously contact-treated with an organoaluminum component [B] and an organosilicon compound component [B] and an organosilicon compound component [C] and an organosilicon compound component [D], A prepolymerized solid can be prepared by polymerizing a limited amount of ethylene or α-olefin. In some cases, the catalyst solid component [A] is replaced with an organoaluminum component [B], an organosilicon compound component [B], an organosilicon compound component [C], and an organosilicon compound component without polymerizing ethylene or α-olefin. A pretreated solid contacted with [D] can be prepared.

In the present invention, when the prepolymerized solid or the pretreated solid is used as a solid catalyst component in the main polymerization, the components [C] and [D] can be omitted in the main polymerization.

The contact treatment of the present invention includes components [A],
The component [B], the component [C] and the component [D] are mixed and reacted usually at 0 to 100 ° C. for 0.1 to 10 hours. The order of mixing the components is not particularly limited, but usually the order of component [A], component [B], component [C] and component [D] is preferable. After the contact treatment, the solid is washed with an inert hydrocarbon solvent such as n-heptane, filtered and separated, and used as a catalyst solid component for prepolymerization or main polymerization.

The prepolymerization in the present invention can be performed by a gas phase method, a slurry method, a bulk method, or the like. The solid obtained in the prepolymerization can be used after the separation in the main polymerization, or the main polymerization can be carried out without separation.

The prepolymerization time is usually from 0.1 to 10 hours, and it is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the solid catalyst component. If the amount is less than 0.1 g per 1 g of the solid catalyst component, the main polymerization activity is not sufficient and the amount of catalyst residues increases, and the stereoregularity of the α-olefin polymer is not sufficient. Also, 100
If it exceeds g, the polymerization activity and the crystallinity of the α-olefin polymer tend to decrease. The prepolymerization temperature is from 0 to 1
The reaction is carried out at 00 ° C, preferably 10 to 70 ° C, in the presence of each catalyst component. When prepolymerization is carried out at a temperature higher than 50 ° C., it is preferable to reduce the concentration of ethylene or α-olefin or to shorten the polymerization time. Otherwise, it is difficult to control the production of 0.1 to 100 g of the prepolymer per 1 g of the solid catalyst component, and the polymerization activity may be reduced in the main polymerization or the crystallinity of the obtained α-olefin polymer may be reduced. Or decrease.

The amount of the organoaluminum compound component [B] used in the prepolymerization is usually such that the molar ratio of Al / Ti to titanium atom of the solid catalyst component [A] is 0.5 to 1000, preferably 1 to 100. It is. The amount of the mixed component of the organosilicon compound component [C] and the organosilicon compound component [D] is usually S with respect to the aluminum atom of the component [B].
i / Al molar ratio of 0.01 to 1, preferably 0.08
０．５0.5. At the time of prepolymerization, hydrogen can be allowed to coexist as necessary.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used to produce the α-olefin polymer having the desired stereoregularity, melting point and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions. ~ 3
Range.

In the method for polymerizing an α-olefin according to the present invention, the organic silicon compound components [C] and [D] are added in addition to the organic aluminum compound component [B] during the main polymerization of the α-olefin. Further, the polymerization activity and the stereoregularity of the polymer can be improved.

In the present invention, examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methylpentene-1, 1-octene and the like. In the present invention, in order to lower the heat sealing temperature of the film, a small amount of ethylene or other α-olefin is copolymerized in the polymerization of α-olefin for the purpose of lowering the melting point or increasing the transparency of the film. Can also.

In order to increase the low-temperature impact strength of a molded article made of an α-olefin polymer, a so-called block copolymer is obtained by further copolymerizing the α-olefin and ethylene after the above-mentioned polymerization and copolymerization of the α-olefin. Can also be manufactured.

The catalyst system of the present invention has a high catalytic activity and the obtained α-olefin polymer has a high stereoregularity and a wide molecular weight distribution. The molecular weight distribution is GP
The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained in terms of polystyrene in the C measurement is 10 or more, more preferably 12 or more, and particularly preferably 15 or more.

The α-olefin polymer obtained in the present invention has a high melt viscoelasticity due to its wide molecular weight distribution, and is particularly excellent in film formability such as a film.
It has excellent mechanical properties such as heat resistance and tensile strength, and does not have the problem of poor appearance of a molded product represented by a flow mark. The α-olefin polymer obtained in the present invention is used not only alone, but also as a compounding material, other plastics, blends with elastomers, glass fibers, and inorganic or organic fillers such as talc, reinforcing agents for organic fillers, Other crystal nucleating agents can be mixed and used, and there is no particular limitation for automobiles,
Excellent performance as a structural material for home appliances.

[0090]

According to the present invention, when an α-olefin is polymerized using the catalyst of the present invention, an α-olefin polymer having high polymerization activity, high stereoregularity and a wide molecular weight distribution can be produced. . Furthermore, in the copolymerization with ethylene or another α-olefin, a copolymer having good randomness and high melt viscoelasticity can be produced.

The α-olefin polymer obtained in the present invention has the same molecular weight distribution as the α-olefin polymer obtained with a conventional titanium trichloride type catalyst having a low polymerization activity, which is called a second generation catalyst. Therefore, the moldability is good and there is no problem such as poor appearance of a molded article such as a flow mark. Therefore, the catalyst system used in the present invention can be used as a substitute for the titanium trichloride type catalyst, and has a very high polymerization activity as compared with the titanium trichloride type catalyst. Step of removing the catalyst residue of, that is, the deashing step using a large amount of organic solvent can be omitted,
This is useful for simplifying the polymerization process and reducing the production cost.

[0092]

Embodiments of the present invention will be described below. In the examples, “polymerization activity” refers to α-
It is the yield (Kg) of the olefin polymer.

Melt fluidity (MFR) was measured according to ASTM-D1.
Represents the weight (g) of the molten polymer at 230 ° C. under a load of 2.16 Kg for 10 minutes measured according to 238.
H. I indicates the ratio (weight of insoluble polymer / weight of charged polymer × 100) when the polymer was subjected to an extraction test with boiling n-heptane for 6 hours. Melting point (Tm) is DSC (SSC-5200 DSC-220C manufactured by Seiko Instruments Inc.)
It measured using. The measurement method was as follows: 10 mg of a sample was heated from 23 ° C. to 230 ° C. at a rate of 10 ° C./min.
After holding for 30 minutes, the temperature was lowered from 230 ° C. to 40 ° C. at a rate of 5 ° C./min.
And the melting point was measured.

The isopentad fraction (mmm) was determined by examining the microtacticity, which is an index of the tacticity of the polymer.
m)% is Macromol in propylene polymer
calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Eucules 8,687 (1975). ^{The 13} C-NMR spectrum is EX-40 manufactured by JEOL Ltd.
Sample 9 in an NMR tube with a diameter of 5 mm
0 mg was added, and 0.75 ml of orthodichlorobenzene was added. The mixture was sealed under a N ₂ atmosphere, heated and dissolved. TM
The measurement was carried out at a temperature of 130 ° C. and the number of scans of 8000 based on S.

The molecular weight distribution was measured using GPC (Waters 150CV type) using polystyrene as a standard substance.
Orthodichlorobenzene solvent, column SHODEX,
(Temperature 145 ° C., concentration 0.05 wt%), the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn, Z
Ratio Mz / Mw of average molecular weight Mz and weight average molecular weight Mw
Was evaluated by.

Reference Example (Synthesis Method of Organosilicon Compound Component [D] Synthesis Example: A stirrer was placed in a 200 mL three-necked flask equipped with a bis (perhydroisoquinolinodimethoxysilane) dropping funnel. After inserting a piece and using a vacuum pump to sufficiently purge the inside of the flask with nitrogen, the flask was charged with 100 mL of distilled and dehydrated n-heptane and 17.9 m of decahydroisoquinoline.
L (0.12 mol), and 1.6 ml in the dropping funnel.
M butyllithium hexane solution 75 mL (0.12 m
ol). While keeping the temperature inside the flask at 4 ° C,
The butyllithium solution in the dropping funnel was slowly dropped into the flask. After completion of the dropwise addition, stirring was continued at room temperature for 12 hours to obtain a lithium salt of perhydroisoquinoline.

Next, a stirrer peak was placed in a flask (capacity: 400 mL) equipped with a glass filter equipped with a dropping funnel.
After the flask was sufficiently purged with nitrogen using a vacuum pump, 60 mL of distilled and dehydrated n-heptane and 9 mL of tetramethoxysilane (0.06 mol
1), and the lithium salt of perhydroisoquinoline was placed in the dropping funnel. At room temperature, the lithium salt of perhydroisoquinoline in the dropping funnel was slowly dropped into the flask. After completion of the dropwise addition, stirring was continued at 40 ° C. for 2 hours, and further, stirring was performed at room temperature for 12 hours. After confirming that the target product was produced by gas chromatography, the precipitate was filtered. The solvent in the filtrate is sufficiently distilled off under reduced pressure, and then the product is purified by primary and secondary distillation to obtain the desired product, bis (part
(Hydroisoquinolino) dimethoxysilane was obtained. This compound has a boiling point of 180 ° C./1 mmHg and a GC purity of 98.5.
%Met.

Example 1 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride was added to 40 mL of toluene.
And then add methyltriethoxysilane 15 mm
ol was added dropwise with stirring, and after completion of the addition, the mixture was reacted at 25 ° C. for 1 hour. After cooling the reaction product to −5 ° C., 18 mL of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, and the temperature of the reaction solution was within the range of −5 to 0 ° C. Kept.
After completion of the dropwise addition, the temperature was gradually raised, and the reaction was continued at 30 ° C. for 1 hour. The precipitated solid was separated by filtration and washed with toluene and n-heptane. Next, 4.9 g of the obtained solid was added to toluene 3
0 mL, and the suspension is added with titanium tetrachloride 150 m
and 3.3 mmol of di-n-heptyl phthalate, and reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off and washed with toluene and then with n-heptane. Further, the solid was suspended again in 30 mL of toluene,
Add 150 mmol of titanium tetrachloride and stir at 90 ° C
For 1 hour. At the same temperature, the solid was filtered off, and the solid was washed with toluene and then with n-heptane. The titanium content in the obtained catalyst solid component was 3.45% by weight.

(3) Polymerization of Propylene In a 2-liter stainless steel autoclave equipped with a stirrer, 2.2 mmol of triethylaluminum as component [B] and di (cyclopentyl) as component [C] under a nitrogen atmosphere. ) 0.04 mmol of dimethoxysilane, 0.32 mmol of bis (perhydroisoquinolino) dimethoxysilane as component [D], and 0.1% of n-heptane slurry of the above catalyst component [A] in terms of titanium atom.
005 mmol, then 0.12 MPa of hydrogen,
1.2 L of liquefied propylene was introduced. The autoclave was cooled to 10 ° C., and stirring was started to carry out prepolymerization for 10 minutes.
Subsequently, the inside of the autoclave was heated to 70 ° C.
Polymerization was carried out at 0 ° C. for 1 hour. After completion of the polymerization, unreacted propylene gas was released, and the polymer was dried under reduced pressure at 60 ° C. for 12 hours to obtain a white powdery polypropylene. Table 1 shows the results
It was shown to.

Example 2 0.06 mmol of di (cyclopentyl) dimethoxysilane was used as the component [C], and 0.3 mmmo of bis (perhydroisoquinolino) dimethoxysilane was used as the component [D].
The same procedure was performed as in Example 1 except that 1 was added. Table 1 shows the results
It was shown to.

Example 3 0.1 mmol of di (cyclopentyl) dimethoxysilane as component [C] and 0.26 mmol of bis (perhydroisoquinolino) dimethoxysilane as component [D]
The same procedure was performed as in Example 1 except that 1 was added. Table 1 shows the results
It was shown to.

Comparative Example 1 Bis (perhydroisoquinolino) dimethoxysilane was used as the component [D] in an amount of 0.36 mmol without the component [C].
The procedure was performed in the same manner as in Example 1 except that 1 was used. Table 1 shows the results
It was shown to.

Comparative Example 2 The procedure of Example 1 was repeated, except that 0.36 mmol of di (cyclopentyl) dimethoxysilane was used as the component [C] and the component [D] was not used. The results are shown in Table 1.

Comparative Example 3 0.04 mmol of di (cyclohexyl) dimethoxysilane was used as the component [C], and 0.36 m of bis (perhydroisoquinolino) dimethoxysilane was used as the component [D].
The procedure was performed in the same manner as in Example 1 except that mol was used. The results are shown in Table 1.

[0105]

[Table 1]

[0106]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a flowchart showing a preparation process and a polymerization method of a catalyst component of the present invention.

Continued on the front page F term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A BA01A BA02A BA03B BB00A BB01B BC06A BC15B BC25B BC34A BC34B BC39B CA16A CA18A CA19A CB33A CB44A DA01 DA02 DA03 FA04 EB01 EA01 ED01 GA06 GA12

Claims (2)

[Claims] 1. [A] A solid catalyst component which essentially contains magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, [C] di (cyclopentyl) dimethoxysilane, and [D] a general formula Organosilicon compound component represented by (1) (However, in (1), R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.) A polymerization method for an α-olefin, comprising polymerizing or copolymerizing an α-olefin in the presence of a catalyst comprising: 2. An α-olefin polymer produced by the polymerization method according to claim 1.