JPH11269219A - α-olefin polymerization method, polymerization catalyst evaluation apparatus and recording medium - Google Patents

Abstract

(57) [Problem] To provide an α-olefin polymer having a wide molecular weight distribution while maintaining high stereoregularity and a high melting point. SOLUTION: [A] A catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B]
A method of polymerizing an α-olefin in the presence of a catalyst comprising an organoaluminum compound component and [C] an organosilicon compound component, wherein the most stable structure of the organosilicon compound satisfies the following formula (1). Α characterized by
-A method of polymerizing olefins. PMI ≧ 600 (1) (However, PMI is the main inertia moment of the most stable structure of the organosilicon compound component.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α-olefin having high activity, high stereoregularity and a wide molecular weight distribution by using one kind of organosilicon compound having a specific structure as a novel catalyst component. Or 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. In order to improve this problem, JP-A-63-245408, JP-A-2-232207, JP-A-4-370103, etc.
A method of expanding the molecular weight distribution by polymerization using a plurality of polymerization vessels or multistage polymerization is disclosed. 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. In the case of a polymerization reactor having a pressure resistance limit, the polymerization temperature must be lowered, and there is a problem that the production speed is adversely affected.

Japanese Patent Application Laid-Open Nos. Hei 3-7703, Hei 4-136006, and Hei 8-301920 disclose different M.P. F. R. A polymerization method is disclosed in which at least two kinds of organosilicon compounds which give the following are used as catalyst components, but either one of the catalyst components often acts, and the effect of expanding the molecular weight distribution is not sufficient. Further, in this method, it is essential to use two or more types of catalyst components, so that the polymerization process, the polymerization apparatus, and the polymerization operation become more complicated.

[0005] Japanese Patent Application Laid-Open Nos. 8-1220021, 8-143621, 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.

Further, 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 high crystallinity is prepared by previously producing a high-crystallinity low-molecular-weight propylene polymer and a high-crystalline high-molecular-weight propylene polymer by a conventional method. Then, a method of melt-mixing them at a desired ratio is conceivable, but also in this case, if an attempt is made to produce a propylene polymer having a relatively low molecular weight and a wide molecular weight distribution, a low molecular weight propylene polymer and a high molecular weight propylene It is very difficult to uniformly melt-mix the polymer, and gel formation becomes a problem.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides an α-olefin polymer having a wide molecular weight distribution while maintaining high stereoregularity and a high melting point. With the goal.

[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] an organosilicon compound component. Wherein the most stable structure of the [C] organosilicon compound satisfies the relationship of the following formula: About. PMI ≧ 600 (where PMI is the main inertia moment of the most stable structure of the organosilicon compound component.)

In the present invention, it is preferable to carry out the main polymerization of the α-olefin after the preliminary polymerization. Further, an organosilicon compound satisfying the above-mentioned relationship of PMI ≧ 600 (where PMI is the main inertia moment of the most stable structure of the organosilicon compound component) is a compound having a polycyclic amino group having 7 or more carbon atoms. It is preferred that the compound has an aminoalkoxysilane.

In the present invention, the above PMI ≧
The aminoalkoxysilane satisfying the relationship of 600 (where PMI is the main inertia moment of the most stable structure of the organosilicon compound component) is an organosilicon compound represented by (1) or (2). Is preferred.

[Formula 2] (However, in (1) or (2), R1 has 1 to 1 carbon atoms.
8 represents a hydrocarbon group, and R ² represents a hydrocarbon group having ² to 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or 1 carbon atom.
Shows the 24 hydrocarbon alkoxy group, R ³ N represents a polycyclic amino group having 7 or more carbon atoms in a backbone together with a nitrogen atom. )

Further, the present invention provides a catalyst comprising: [A] a solid catalyst component essentially containing magnesium, titanium, a halogen element and an electron donor; [B] an organoaluminum compound component; and [C] an organosilicon compound component. A method for polymerizing an α-olefin in the presence of a catalyst, comprising: (A) an input device for inputting the structure of the organosilicon compound component; (b) a first arithmetic device for calculating the most stable structure of the organosilicon compound component input to the input device; (c)
The second arithmetic unit for calculating the main inertia moment using the most stable structure obtained by the first arithmetic unit, the most stable structure obtained by the first arithmetic unit, and the second arithmetic unit A storage device for storing the obtained main moment of inertia, and (f) a display device

Further, the present invention relates to the above (a) to
The present invention relates to a computer-readable recording medium on which a program for realizing the function (e) is recorded.

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a solid catalyst component essentially comprising 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 and JP-A-56-55405.
JP, JP-A-56-45909, JP-A-56-45909
No. 163102, JP-A-57-63310,
JP-A-57-115408, JP-A-58-830
No. 06, JP-A-58-83016, JP-A-58-83016
JP-A-8-138707, JP-A-59-149905, JP-A-60-23404, JP-A-60-3
The methods proposed in JP 2805, JP-A-61-18330, JP-A-61-55104, JP-A-2-77413, JP-A-2-117905 and the like can be used.

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. (2) A magnesium compound and an electron donor are dissolved in a solvent, and the titanium halide is added to the solution. A method of adding a compound to precipitate a catalyst solid, and the like can be mentioned.

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 dimethyl. Diethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane,
Trimethylmonoethoxysilane and trimethylmonobutoxysilane can be exemplified. Particularly, methylphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane are preferable.

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, and ethyl ethyl chloride. 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 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 the titanium halide compound and the electron donor. , And then a treatment with a titanium halide compound.

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 titanium halide is used without using an inert solvent. Disperse the solid in the 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 that can be used 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-n-orthophthalate.
Heptyl, di-n-octyl orthophthalate and the like can be mentioned. Further, as the electron donor, two or more ether groups as disclosed in JP-A-3-706, JP-A-3-62805, JP-A-4-270705, and JP-A-6-25332 are used. Compounds having the formula (I) can also be preferably used.

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

As the component [B] of the present invention, alkylaluminum, alkylaluminum halide and the like can be used. Alkylaluminum is preferable, and trialkylaluminum is particularly preferable. Specific examples thereof include trimethylaluminum and 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 component [B] used as the polymerization catalyst for the α-olefin is determined by the element ratio (Al / Al) of the component [B] to the titanium (Ti) of the component [A].
Ti), 0.1 to 500, preferably 0.5 to 150
It is.

The main inertia moment PMI of the most stable structure of the organosilicon compound of the component [C] of the present invention is in the range of PMI
≧ 600, preferably PMI ≧ 900, more preferably PMI ≧ 1,000. Further, the upper limit of PMI is preferably 5,000, more preferably 4,000.
And particularly preferably 3,000. The main moment of inertia of the most stable structure of the organosilicon compound component can be calculated by a computer including the following components.

That is, (a) an input device for inputting the structure of the organosilicon compound component, (b) a first arithmetic device for calculating the most stable structure of the organosilicon compound component input to the input device, (c) A) a second arithmetic unit for calculating a main inertia moment using the most stable structure obtained by the first arithmetic unit, a most stable structure obtained by the first arithmetic unit,
And a storage device for storing the main inertia moment obtained by the second arithmetic device, and (f) a calculation device including a display device.

The above computing device will be described with reference to FIG. FIG. 1 is a block diagram illustrating an example of a configuration of a computing device. This is an example of a computing device including an input device 1, a first computing device 11, a second computing device 12, a storage device 2, and a display device 3.

As the input device 1, a graphic input device such as a light pen or an image reader, a punch card reader, or the like can be used in addition to the keyboard. Two or more of these devices can be used in combination.

As the arithmetic units 11 to 12, so-called personal computers can be used as CPUs. In addition, if necessary, a mini computer or super
A computer or the like can also be used.

As the storage device 2, a floppy disk, a hard disk, a tape, or the like can be used.

As the display device 3, a cathode ray tube, a liquid crystal display, various printers, plotters and the like are suitably used. These may be used in combination.

Hereinafter, the operation of each component of the above-described computing device will be described in detail.

The input device is a device for inputting the chemical structure of the organosilicon compound component. For the chemical structure,
It may be input as graphic information, and each atom group such as methylene group, methyl group, substituted methylene group, alkyl group, phenylene group, phenyl group, or amide bond or ester bond which can constitute each chemical structure A number may be given and input may be made by a combination of the numbers. Alternatively, spatial coordinates in an existing database may be input.

The first arithmetic unit 11 calculates the most stable structure of the organosilicon compound component. As a technique used in this case, a molecular mechanics method, a semi-empirical molecular orbital method, an ab initio molecular orbital method, or the like is used. Among them, the molecular mechanics method is suitably used.

The second arithmetic unit 12 calculates the principal inertia moment (PMI) of the most stable structure of the organosilicon compound component based on the most stable structure of the organosilicon compound component obtained by the arithmetic unit 11. .

As a specific compound of the component [C] of the present invention, an organosilicon compound represented by the general formula (1) or (2) can be mentioned.

[0037]

Embedded image (However, in (1) or (2), R ¹ has 1 to ¹ carbon atoms.
8 represents a hydrocarbon group, and R ² represents a hydrocarbon group having ² to 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or 1 carbon atom.
Shows the 24 hydrocarbon alkoxy group, R ³ N represents a polycyclic amino group having 7 or more carbon atoms in a backbone together with a nitrogen atom. )

R ¹ is a hydrocarbon group having 1 to 8 carbon atoms,
Examples thereof include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a ter-butyl group, a sec-butyl group, an n-pentyl group, and an iso-pentyl group. , Cyclopentyl group, n-hexyl group, cyclohexyl group and the like. Particularly preferred is a methyl group.

R ² has ² to 24 carbon atoms, preferably 2 to 8 carbon atoms.
A hydrocarbon group of 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, or 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms.
To 8 hydrocarbon alkoxy groups. Among them, carbon number 2
To 24 hydrocarbon groups or C2 to C24 hydrocarbon amino groups are preferred.

Specific examples of the hydrocarbon group having 2 to 24 carbon atoms include ethyl group, n-propyl group, iso-propyl group,
n-butyl group, isobutyl group, sec-butyl group, ter
-Butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, texyl, phenyl, benzyl, toluyl and the like. Further, a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group may be mentioned.

Specific examples of the hydrocarbon amino group having 2 to 24 carbon atoms include a dimethylamino group, a methylethylamino group,
Diethylamino group, ethyl n-propylamino group, di-n
-Propylamino group, ethylisopropylamino group, diisopropylamino group, pyrrolidino group, piperidino group,
Hexamethyleneimino group and the like. Carbon number 1
Specific examples of the 24 hydrocarbon alkoxy groups include a methoxy group, an iso-propoxy group, a ter-butoxy group and the like. Among the above, n-propyl group, iso-
A propyl group such as a propyl group, a butyl group such as an isobutyl group, a diethylamino group, and the like are preferably used.

R ³ N is a polycyclic amino group having 7 or more, preferably 7 to 40, more preferably 7 to 20 carbon atoms forming 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 part or all 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 ³ NH is removed and Si and N are chemically bonded. In the general formula (1), the two R ³ N groups may be the same or different.

As specific examples of R ³ NH, as shown in the following chemical structural formula, perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazoline , Perhydroacridine, perhydrophenanthridine, perhydrobenzo
(g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline ,
Amine compounds such as perhydroaceisoquinoline and perhydroiminostilbene, and a part of hydrogen atoms other than nitrogen atoms in the amine compound are alkyl groups,
Examples thereof include amine compounds substituted with a phenyl group or a cycloalkyl group.

[0044]

[Formula 4]

Particularly preferred R ³ NH include perhydroquinoline, perhydroisoquinoline and derivatives thereof.

The organosilicon compound represented by the general formula (1) includes a perhydroquinolino compound represented by the general formula (4), a perhydroisoquinolino compound represented by the general formula (5), (Per-hydroquinolino) (per-hydroisoquinolino) compounds represented by the formula (6).

[0047]

[Formula 5]

R ⁴ represents a substituent on the saturated ring of R ³ N;
It is hydrogen or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred as R ⁴ is hydrogen,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a ter-butyl group, and a sec-butyl group. Further, the number of hydrocarbon substituents on the saturated ring of R ³ N may be one or more.

The compound represented by the general formula (4) 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-hydroquinolino) 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
-Dimethylper-hydroquinolino) dimethoxysilane, bis (5.7-dimethylper-hydroquinolino) dimethoxysilane, bis (5,8-dimethylper-hydroquinolino)
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-dimethylpar-
(Hydroquinolino) dimethoxysilane, bis (7,8-dimethylperhydroquinolino) dimethoxysilane, bis (7,9-dimethylperhydroquinolino) dimethoxysilane, bis (7,10-dimethylperhydroquinolino)
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.

Also, (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,
Hydroquinolino) (10-methylpa-hydroquinolino)
Examples include compounds such as dimethoxysilane.

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

As the compound represented by the general formula (5),
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-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,5-dimethylperhydroisoquinolino) 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-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,5-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,6-dimethylpa-hydroisoquinolino) dimethoxysilane , Bis (4,7-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4
9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,6-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,7-
Dimethyl per-hydroisoquinolino) dimethoxysilane,
Bis (5,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis ( 6,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,9-dimethylpar-
Hydroisoquinolino) dimethoxysilane, bis (6.1
0-dimethylperhydroisoquinolino) dimethoxysilane, bis (7,8-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (7,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (8,9-dimethylper-hydroisoquinolino) dimethoxysilane Bis (dimethyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as bis (8,10-dimethylper-hydroisoquinolino) dimethoxysilane and bis (9,10-dimethylper-hydroisoquinolino) dimethoxysilane. Can be

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) Isoquinolino)
Examples include bis (trimethyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as dimethoxysilane.

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 preferred.

The compound represented by the general formula (6) includes
(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-methylperhydroquinolino) (perhydroisoquinolino) 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.

Also, perhydroindolino compounds, perhydroisoindolino compounds, 1,2,3,4-tetrahydroquinolino compounds, 1,2,3,4-tetrahydroisoquinolino compounds, (1,2, 3,4-tetrahydroquinolino) (1,2,3,4-
Tetrahydroisoquinolino) compounds and the like.

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

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

[0065]

[Formula 6]

[0066]

Embedded image

Examples of the organosilicon compound represented by the general formula (2) include a perhydroquinolino compound represented by the general formula (7) and a perhydrohydroquinolino compound represented by the general formula (8). No.

[0068]

[Formula 8]

R ⁴ represents a substituent on the saturated ring of R ³ N;
It is hydrogen or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred as R ⁴ is hydrogen,
Examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a ter-butyl group and a sec-butyl group. Also, R ³
The number of hydrocarbon substituents on the saturated ring of N may be one or more.

The compound represented by the general formula (7) includes
Ethyl (perhydroquinolino) dimethoxysilane, n-
Propyl (perhydroquinolino) dimethoxysilane, i
So-propyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, isopropyl (perhydroquinolino) dimethoxysilane, ter-butyl (perhydroquinolino) dimethoxysilane, sec-butyl (per- Hydroquinolino)
Dimethoxysilane, n-pentyl (perhydroquinolino) dimethoxysilane, iso-pentyl (perhydroquinolino) dimethoxysilane, cyclopentyl (perhydroquinolino) dimethoxysilane, n-hexyl (particulate
(Hydroquinolino) dimethoxysilane, cyclohexyl (perhydroquinolino) dimethoxysilane, texyl (perhydroquinolino) dimethoxysilane, n-octyl (perhydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, piperidino (pa-hydroquinolino) dimethoxy Perhydroquinolinosilane compounds such as silane and diethylamino (perhydroquinolino) dimethoxysilane are exemplified.

Ethyl (2-methylperhydroquinolino)
Dimethoxysilane, n-propyl (2-methylper-hydroquinolino) dimethoxysilane, iso-propyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Butyl (2-methylperhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane, ter-butyl (2-methylper
Hydroquinolino) dimethoxysilane, sec-butyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Pentyl (2-methylpa-hydroquinolino) dimethoxysilane, iso-pentyl (2-methylpa-hydroquinolino) dimethoxysilane, cyclopentyl (2-methylpa-hydroquinolino) dimethoxysilane, n-hexyl (2-methylpa-hydroquinolino) dimethoxysilane,
Cyclohexyl (2-methylperhydroquinolino) dimethoxysilane, texyl (2-methylperhydroquinolino) dimethoxysilane, n-octyl (2-methylpar-
2- (hydroquinolino) dimethoxysilane and phenyl (2-methylperhydroquinolino) dimethoxysilane
Methyl perhydroquinolinosilane compound is exemplified.

Iso-propyl (3-methylperhydroquinolino) dimethoxysilane, iso-propyl (4-
Methyl per-hydroquinolino) dimethoxysilane, iso
-Propyl (5-methylperhydroquinolino) dimethoxysilane, iso-propyl (6-methylperhydroquinolino) dimethoxysilane, iso-propyl (7-methylperhydroquinolino) dimethoxysilane, iso-
Examples include methyl-substituted perhydroquinolinosilane compounds such as propyl (8-methylperhydroquinolino) dimethoxysilane, iso-propyl (9-methylperhydroquinolino) dimethoxysilane, and iso-propyl (10-methylperhydroquinolino) dimethoxysilane.

Among the above compounds, ethyl (per-hydroquinolino) dimethoxysilane, n-propyl (per-hydroquinolino) dimethoxysilane, iso-propyl (per-hydroquinolino) dimethoxysilane, n-butyl (per-hydroquinolino) dimethoxysilane , Iso-butyl (perhydroquinolino) dimethoxysilane, ter
-Butyl (perhydroquinolino) dimethoxysilane, se
c-butyl (perhydroquinolino) dimethoxysilane,
Compounds such as n-hexyl (per-hydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, and diethylamino (per-hydroquinolino) dimethoxysilalane are preferred.

As the compound represented by the general formula (8),
Ethyl (perhydroisoquinolino) dimethoxysilane,
n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroiso Quinolino) dimethoxysilane, ter-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n
-Pentyl (per-hydroisoquinolino) dimethoxysilane, iso-pentyl (per-hydroisoquinolino) dimethoxysilane, cyclopentyl (per-hydroisoquinolino) dimethoxysilane, n-hexyl (per-hydroisoquinolino) Dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, texil (part
(Hydroisoquinolino) dimethoxysilane, n-octyl (per-hydroisoquinolino) dimethoxysilane, phenyl (per-hydroisoquinolino) dimethoxysilane, piperidino (per-hydroisoquinolino) dimethoxysilane,
Perhydroisoquinolinosilane compounds such as diethylamino (per-hydroisoquinolino) dimethoxysilane are exemplified.

Ethyl (2-methylperhydroisoquinolino) dimethoxysilane, n-propyl (2-methylper
(Hydroisoquinolino) dimethoxysilane, iso-propyl (2-methylperhydroisoquinolino) dimethoxysilane, n-butyl (2-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (2-methylperhydroiso) Quinolino) dimethoxysilane, ter-
Butyl (2-methylperhydroisoquinolino) dimethoxysilane, sec-butyl (2-methylperhydroisoquinolino) dimethoxysilane, n-pentyl (2-methylperhydroisoquinolino) dimethoxysilane, iso-
Pentyl (2-methylperhydroisoquinolino) dimethoxysilane, cyclopentyl (2-methylperhydroisoquinolino) dimethoxysilane, n-hexyl (2-methylperhydroisoquinolino) dimethoxysilane, cyclohexyl (2-methylpara (Hydroisoquinolino) dimethoxysilane, texyl (2-methylperhydroisoquinolino) dimethoxysilane, n-octyl (2-methylperhydroisoquinolino) dimethoxysilane, phenyl (2-methylperhydroisoquinolino) dimethoxy Examples thereof include 2-methyl perhydroisoquinolinosilane compounds such as silane.

Iso-propyl (3-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (4-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (5-methylperhydroisoquinolino) dimethoxysilane Iso-propyl (6-methylperhydroisoquinolino) dimethoxysilane, iso
-Propyl (7-methylper-hydroisoquinolino) dimethoxysilane, iso-propyl (8-methylper-hydroisoquinolino) dimethoxysilane, iso-propyl (9-methylper-hydroisoquinolino) dimethoxysilane, iso-propyl Examples include methyl-substituted perhydroisoquinolinosilane compounds such as (10-methylperhydroisoquinolino) dimethoxysilane.

Among the above compounds, ethyl (per-hydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (per-hydroisoquinolino) dimethoxysilane,
n-butyl (per-hydroisoquinolino) dimethoxysilane, iso-butyl (per-hydroisoquinolino) dimethoxysilane, ter-butyl (per-hydroisoquinolino)
Dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (per-hydroisoquinolino) dimethoxysilane, diethylamino (per-hydroisoquino) Compounds such as (rino) dimethoxysilalane are preferred.

Specific examples of the organosilicon compound represented by the general formula (2) include compounds represented by the following chemical structural formulas.

[0079]

[Formula 9]

[0080]

[Formula 10]

The organosilicon compound component [C] 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] represented by the general formula (2) can be synthesized by an equivalent reaction of an alkyltrimethoxysilane or an alkylchlorodimethoxysilane with a magnesium or lithium salt of an HNR secondary amine.

The amount of the component [C] used is determined by the element ratio (Si / Si) of the component [C] silane to the aluminum component [B].
Al) is preferably from 0.01 to 1.0, particularly preferably from 0.05 to 1.0.
0.33 is preferred.

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, and usually, the hydrogen partial pressure is 0.05. ~ 3.
It is in the range of 0.

In the present invention, when the α-olefin is polymerized,
The order of contact of the catalyst components is not particularly limited, but the components [A] and [C] are contacted in advance after the components [A] and [B] or the components [B] and [C] are contacted in advance. Preferably.

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 enhance the low-temperature impact strength of a molded article made of an α-olefin polymer, a so-called block copolymer in which α-olefin and ethylene are further copolymerized after the above-mentioned polymerization and copolymerization of α-olefin. Can also be manufactured.

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 used as a solvent and polymerized therein is employed. 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,
The polymerization temperature is from 10 to 150 ° C, preferably from 30 to 100 ° C.
° C, particularly preferably from 60 to 90 ° C. The polymerization time is in the range of usually 0.1 to 10 hours, preferably 0.5 to 7 hours. This catalyst has high polymerization activity, especially at a high polymerization temperature of 70 ° C. or higher, has high stereoregularity, and has a wide molecular weight distribution α.
An olefin polymer can be obtained.

In the present invention, ethylene or α-
It is preferred 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 an improvement in polymerization activity, an improvement in stereoregularity of the polymer, and a stabilization of the particle shape of the polymer. As a method of the pre-polymerization, the catalyst solid component [A] is previously added to the organoaluminum compound component [B].
And a contact treatment with the organosilicon compound component [C], and washing the solid to prepare a pre-treated solid. Further, using the component [A] or the above pre-treated solid,
A prepolymerized solid can be prepared by polymerizing a limited amount of ethylene or α-olefin in the presence of component [B] and component [C].

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

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

The prepolymerization in the present invention can be carried out 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, the amount of catalyst residue increases, and the stereoregularity of the α-olefin polymer is not sufficient. If it exceeds 100 g, the polymerization activity and the crystallinity of the α-olefin polymer tend to decrease. The prepolymerization temperature is 0 to 100 ° C, preferably 10 to 90 ° C, in the presence of each catalyst component. 5
When performing prepolymerization at a temperature higher than 0 ° C.,
Reduce the ethylene or α-olefin concentration,
It is preferable 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 0.5 to 1000, preferably 1 to 100, in terms of the molar ratio of Al / Ti to titanium atoms in the solid catalyst component. The amount of the organosilicon compound component [C] used is usually S with respect to the aluminum atom of the component [B].
i / Al molar ratio is 0.01 to 1, preferably 0.08 to 0.1.
5 At the time of prepolymerization, hydrogen can be allowed to coexist as necessary.

The present catalyst system has a high catalytic activity, and the resulting α-olefin polymer has a high stereoregularity and a high melting point.
Wide molecular weight distribution. Regarding the molecular weight distribution, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn measured in terms of polystyrene in GPC measurement is 12 or more, more preferably 14 or more. The α-olefin polymer of the present invention has high crystallinity and a wide molecular weight distribution,
Excellent mechanical properties such as heat resistance and tensile strength, and high die swell value for shear rate during melting,
There is no problem of poor appearance of the molded product such as a flow mark. The α-olefin polymer of the present invention is used not only alone, but also as a compound material, other plastics,
Blend with elastomer, further glass fiber,
Inorganic and organic fillers such as talc, and other crystal nucleating agents can be mixed and used, and although not particularly limited, they can exhibit excellent performance as structural materials for automobiles and home appliances.

[0095]

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, high melting point and a wide molecular weight distribution is produced. be able to. Furthermore, in the copolymerization with ethylene or other α-olefin,
A copolymer having good randomness and high viscoelasticity at the time of melting can be produced. Since the α-olefin polymer obtained in the present invention has the same molecular weight distribution as the α-olefin polymer obtained with the conventional titanium trichloride type catalyst called a second generation catalyst having low polymerization activity, it is molded. It has good properties and does not have the problem of poor appearance of molded articles such as flow marks. 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. The step of removing the catalyst residue, that is, the step of deashing using a large amount of an organic solvent, can be omitted, which is extremely useful for simplifying the polymerization process and reducing the production cost.

[Examples] Examples of the present invention will be described below. In Examples, “polymerization activity” refers to 1 g of a catalyst solid.
Of the α-olefin polymer per unit weight (kg).

The melt flowability (MFR) was measured according to ASTM.
230 ° C, 2.16 Kg measured according to -D1238
Represents the weight (g) of the molten polymer for 10 minutes under a load of.

The melting point (Tm) was measured by DSC (ASC-5200 manufactured by Seiko-Electronic Industries). As a measurement condition, in a propylene polymer, 10 mg
The temperature was raised to 230 ° C. at a rate of 10 ° C./min, and held as it was for 5 minutes, then lowered to a temperature of 230 to 40 ° C. at a rate of 5 ° C./min. Was measured for its melting point.

The isopentad fraction (mmmm)%, which is one of the tacticity indexes of the polymer and whose microtacticity was examined, was found to be equal to Macr in the propylene polymer.
Calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on OMOLECULES 8,687 (1975). ^{The 13} C-NMR spectrum was obtained from JEOL E
Using an X-400 apparatus, based on TMS, temperature 13
The measurement was performed at 0 ° C. using an o-dichlorobenzene solvent.

The molecular weight distribution was measured using GPC (Waters 150CV type, o-
Dichlorobenzene solvent, column SHOdex, temperature 14
It was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from 5 ° C. and a concentration of 0.05 wt%).

REFERENCE EXAMPLE The most stable structure of the organosilicon compound shown in Table 1 was calculated by the above-mentioned calculation device (using the molecular mechanics method in the calculation device 11), and the principal moment of inertia (PM
I) was determined. Table 1 shows the results.

Example 1-7, Comparative Example 1-2 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride and 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 mixed with 30 parts of toluene.
mL of titanium tetrachloride.
ol and 3.3 mmol of di-n-heptyl phthalate were added and reacted at 90 ° C. for 1 hour with stirring. The solid was filtered off at the same temperature and washed with toluene and then with n-heptane.
Furthermore, the solid was suspended again in 30 mL of toluene, 150 mmol of titanium tetrachloride was added, and the mixture was stirred at 90 ° C. for 1 hour.
Allowed to react for hours. 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 solid catalyst component was 3.55 wt%. This solid was suspended in 80 mL of heptane to prepare a heptane slurry as a solid catalyst component.

(2) Polymerization of Propylene A glass in which n-heptane slurry (7.9 mg as a solid catalyst component) of the solid catalyst component [A] was sealed in a stainless steel autoclave having a 2 L internal volume equipped with a stirrer. After the ampoule tube was attached, the inside of the autoclave was sufficiently replaced with nitrogen. Next, 2.1 mL of n-heptane solution containing 2.1 mmol of triethylaluminum as the organoaluminum compound component [B], and n-heptane solution 1 containing 0.35 mmol of the compound shown in Table 1 as the organosilicon compound component [C] .74 mL was charged. Then, 0.2MPa
After the introduction of hydrogen, 1.2 L of liquefied propylene was introduced, and the autoclave was shaken. The autoclave was cooled to 10 ° C., and at the same time as the stirring was started, the glass ampule tube containing the solid catalyst component was crushed and prepolymerized for 10 minutes. Subsequently, the inside of the autoclave was heated to 70 ° C, and further heated at 70 ° C for 1 hour.
Polymerization was carried out for hours. After completion of the polymerization, unreacted propylene gas was released, and the polymer was dried under reduced pressure at 50 ° C. for 20 hours to obtain a white powdery polypropylene. Table 5 shows the measurement results of the polymerization activity and the properties of the polymer.

Example 2-7, Comparative Example 1-2 Using the organosilicon compound component [C] shown in Tables 2 to 4, Table 1 was used.
Polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out under the conditions shown in Table 1. Table 5 shows the measurement results of the polymerization activity and the properties of the polymer.

[0105]

【table 1】

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

[Brief description of the drawings]

FIG. 1 is a block diagram illustrating an example of a configuration of a computing device according to the present invention.

FIG. 2 is a flowchart showing a preparation process and a polymerization method of a catalyst component of the present invention.

Claims (6)

[Claims] 1. In the presence of a catalyst consisting of [A] a solid catalyst component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] an organosilicon compound component. A method for polymerizing an α-olefin, wherein the most stable structure of the organosilicon compound satisfies the relationship of the following formula (1).
Olefin polymerization method. PMI ≧ 600 (1) (However, PMI is the main inertia moment of the most stable structure of the organosilicon compound component.) 2. The method according to claim 1, wherein α
-A method for polymerizing α-olefins, comprising performing main polymerization of olefins. An organosilicon compound satisfying the relationship of PMI ≧ 600 (where PMI is the main inertia moment of the most stable structure of the organosilicon compound component) is a polycyclic amino group having 7 or more carbon atoms. 3. The method for polymerizing an α-olefin according to claim 1, wherein the method is an aminoalkoxysilane having the formula: 4. An organosilicon compound satisfying the relationship of PMI ≧ 600 (where PMI is the main inertia moment of the most stable structure of the organosilicon compound component) is represented by the general formula (1) or (2). The method for polymerizing an α-olefin according to claim 1 or 2, wherein the aminoalkoxysilane is represented by the formula (1). [Formula 1] (However, in (1) or (2), R1 has 1 to 1 carbon atoms.
8 represents a hydrocarbon group, and R ² represents a hydrocarbon group having ² to 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or 1 carbon atom.
Shows the 24 hydrocarbon alkoxy group, R ³ N represents a polycyclic amino group having 7 or more carbon atoms in a backbone together with a nitrogen atom. ) [5] [A] a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor, [B]
A method for polymerizing an α-olefin in the presence of a catalyst comprising an organoaluminum compound component and [C] an organosilicon compound component, comprising: (A) an input device for inputting the structure of the organosilicon compound component; (b) a first arithmetic device for calculating the most stable structure of the organosilicon compound component input to the input device; (c)
The second arithmetic unit for calculating the main inertia moment using the most stable structure obtained by the first arithmetic unit, the most stable structure obtained by the first arithmetic unit, and the second arithmetic unit A storage device for storing the obtained main moment of inertia, and (f) a display device 6. A computer-readable recording medium on which a program for realizing the functions (a) to (e) according to claim 5 is recorded.