JPH11147906A - Polymerization of alpha-olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly active, highly stereoregular α-olefinic polymer with a broad mol.wt. distribution by (co)polymerizing an α-olefin in the presence of a catalyst obtd. by contacting c catalytic solid component comprising Mg, Ti, a halogen element and an electron donor, a specific organoaluminum compd. and an organosilicon compd. SOLUTION: A catalyst is obtd. by precontacting a catalytic solid component prepd. by copulverizing a magnesium compd., an electron donor and a titanium halide compd. with an organoaluminum compd. and an organosilicon compd. having formula I or II (wherein R<1> is a 1-8C hydrocarbon group; R<2> is a 2-24C hydrocarbon amino group or a 1-24C hydrocarbon alkoxy group; and R<3> N is a 7-40C polycyclic amino group forming a skeleton together with the nitrogen atom) at 0-70 deg.C for 0.1-10 hrs. An α-olefin is (co)polymerized in the presence of the catalyst in an aim of a hydrogen partial pressure of 0.05-3.0 under a polymerization pressure of 0.1-20 Mpa at a temp. of 10-150 deg.C for 0.1-10 hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel catalyst comprising a single type of organosilicon compound having a specific structure as a novel catalyst component, thereby achieving high activity, high stereoregularity, and a wide molecular weight distribution. The present invention relates to a method for producing a homopolymer of olefin or a copolymer with another α-olefin.

[0002]

2. Description of the Related Art In recent years, in order to polymerize an .alpha.-olefin, a solid catalyst component essentially containing magnesium, titanium, a halogen element and an electron donor, an organometallic compound of a Group I to III group metal, and an electron A highly active supported catalyst system comprising a donor is disclosed in JP-A-57-63310, JP-A-58-83016.
Many proposals have been made in JP-A-59-58010, JP-A-59-58010 and JP-A-60-44507. Further, JP-A-62-11705
JP, JP-A-63-259807, JP-A-2-84404, JP-A-4-202505, JP-A-4-370103, etc., using a specific organosilicon compound as an electron donor A polymerization catalyst characterized by the above is disclosed.

[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, Japanese Patent Application Laid-Open No. 63-245408 and
No. 2-232207, JP-A-4-370103, and the like, by polymerization using a plurality of polymerization vessels, or by multi-stage polymerization,
Methods for expanding the molecular weight distribution are disclosed. But,
Such a method requires a complicated operation and has to lower 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.

[0004] Also, JP-A-3-7703 and JP-A-4-1360
No. 06 and JP-A-8-301920 disclose a polymerization method in which at least two kinds of organosilicon compounds giving different MFRs are mixed and used as a catalyst component. But,
Since either one of the catalyst components often acts, the effect of expanding the molecular weight distribution is not sufficient, and it is necessary to use two or more types of catalyst components. It becomes more complicated.

Further, Japanese Patent Application Laid-Open Nos. 8-120021 and 8-14
JP-A-3621 and JP-A-8-231663 disclose methods using a cyclic aminosilane compound, but these compounds have a problem that the molecular weight distribution is not necessarily wide.

Further, Japanese Patent Application Laid-Open Nos. Hei 6-25336 and Hei 7-90
No. 012, JP-A-7-97411 and the like disclose a method of using a nitrogen-containing heterocyclic-substituted organosilicon compound in which an arbitrary carbon atom in a heterocycle is directly bonded to a silicon atom. However, it does not describe the molecular weight distribution. 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 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. In these cases, a method of melt-mixing them at a desired ratio is conceivable. However, in this case, if a propylene polymer having a relatively low molecular weight and a wide molecular weight distribution is to be produced, a low molecular weight propylene polymer and a high molecular weight It is extremely difficult to uniformly melt and mix the propylene polymer of the formula (1), which causes problems such as gel formation.

[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] a compound represented by the general formula (1) ) Or a method for polymerizing α-olefins in the presence of a catalyst obtained by pre-contacting the organosilicon compound component represented by (2) in the presence of a catalyst.

[0010]

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[0011]

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.
And R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom. )

[0012]

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, JP-A-56-55405, and JP-A-56-55405.
-45909, JP-A-56-163102, JP-A-57-633
No. 10, JP-A-57-115408, JP-A-58-83006, JP-A-58-83016, JP-A-58-138707, JP-A-59-149905, JP-A-60-23404,
JP-A-60-32805, JP-A-61-18330, JP-A
61-55104, JP-A-2-77413, JP-A-2-179
The method proposed in Japanese Patent Publication No. 05 can be adopted.

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) Dissolving a magnesium compound and an 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], the catalyst solid components described in JP-A-60-152511, JP-A-61-31402 and JP-A-62-81405 achieve the effects of the present invention. It is particularly preferred in terms of performing According to the production methods described above, an aluminum halide is reacted with a silicon compound, and a Grignard compound is further reacted to precipitate a solid. Aluminum halide that can be used in the above reaction is
Although anhydrous aluminum halide is preferable, it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water can also be used. Specific examples of aluminum halide include:
Examples thereof 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, dimethyl Diethoxysilane, 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 usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3 in terms of element ratio (Al / Si). It is preferred to use an active solvent. The reaction temperature is usually from 10 to 100 ° C, preferably from 20 to 80 ° C, and the reaction time is usually from 0.2 to 5 hours, preferably from 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, 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 amount of the magnesium compound used is usually 0.5 to 3, preferably 1.5 to 2.3, in terms of the element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound.
Range. The reaction temperature is usually -50 to 100 ° C, preferably -20 to 50 ° C, and the reaction time is usually 0.2 to 5 hours, preferably 0.5 to 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 further treated 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, and dichlorodiethoxytitanium. Butoxytitanium, monochlorotriethoxytitanium and monochlorotributoxytitanium can be mentioned. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferred.

The electron donor used in the above contact treatment is a Lewis basic compound, preferably an aromatic diester, particularly preferably an orthophthalic diester. Specific examples of the orthophthalic acid diester include diethyl orthophthalate, di-n-butyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, di-n-hexyl orthophthalate, di-2-ethylhexyl orthophthalate, di-n-heptyl orthophthalate And di-n-octyl orthophthalate. As electron donors, JP-A-3-706, JP-A-3-6280
Compounds having two or more ether groups, such as those described in JP-A-5, 4-270705, and 6-25332, can also be preferably used.

After the above-mentioned contact treatment, generally, the treated solid is separated from the treated mixture and sufficiently washed 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 organoaluminum compound component [B] of the present invention, alkylaluminum, alkylaluminum halide and the like can be used. Alkylaluminum is preferred, and trialkylaluminum is particularly preferred. , 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 α-olefin polymerization catalyst is 0.1 to 500 in terms of the element ratio (Al / Ti) of titanium in the solid catalyst component [A] to titanium.
, Preferably 0.5 to 150.

The component [C] of the present invention is an organosilicon compound represented by the general formula (1) or (2).

[0027]

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[0028]

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(However, in (1) or (2), R ¹
Represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents a hydrocarbon group having 2 to 2 carbon atoms.
A hydrocarbon group of 24, a hydrocarbon amino group of 2 to 24 carbon atoms or a hydrocarbon alkoxy group of 1 to 24 carbon atoms,
³ N is the number of carbon atoms to form the backbone together with the nitrogen atom 7-4
0 represents a polycyclic amino group. )

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 methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-
Butyl, ter-butyl, sec-butyl, n-pentyl, iso-pentyl, cyclopentyl, n-hexyl, cyclohexyl and the like. Particularly preferred is a methyl group.

R ² is a hydrocarbon group having 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 8 carbon atoms. It is a hydrogen alkoxy group. Among them, those having 2 to 24 carbon atoms
Or a hydrocarbon amino group having 2 to 24 carbon atoms.

Specific examples of the hydrocarbon group having 2 to 24 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, ter-butyl group, and n-butyl group.
Examples include a pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, texyl group, phenyl group, benzyl group, and toluyl group. Also, a trimethylsilylmethyl group,
A hydrocarbon group containing a silicon atom such as a bistrimethylsilylmethyl group is exemplified.

Specific examples of the hydrocarbon amino group having 2 to 24 carbon atoms include a dimethylamino group, a methylethylamino group,
Examples include a diethylamino group, an ethyl n-propylamino group, a di-n-propylamino group, an ethylisopropylamino group, a diisopropylamino group, a pyrrolidino group, a piperidino group, and a hexamethyleneimino group. Carbon number 1-24
Specific examples of the hydrocarbon alkoxy group of the methoxy group,
iso-propoxy group, ter-butoxy group and the like.

Among the above, propyl groups such as n-propyl group and iso-propyl group; butyl groups such as iso-butyl group;
A diethylamino group or the like is preferably used.

R ³ 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 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, perhydrocarbazole, perhydroacridine, perhydrophenidine Nantridine, perhydrobenzo
(g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline,
Perhydroaceisoquinoline, an amine compound such as perhydroiminostilbene, and a part of the hydrogen atom other than the nitrogen atom in the amine compound is an alkyl group,
Examples thereof include amine compounds substituted with a phenyl group or a cycloalkyl group.

[0037]

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As R ³ NH, as shown by the following chemical structural formula, 1,2,3,4-tetrahydroquinoline, 1,2,
A polycyclic amino group in which a part of the ring is unsaturated, such as 3,4-tetrahydroisoquinoline, and an amine compound in which a part of hydrogen atoms other than a nitrogen atom is substituted with an alkyl group, a phenyl group, or a cycloalkyl group. Can be mentioned.

[0039]

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Particularly preferred R ³ NH includes perhydroquinoline, perhydroisoquinoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline and derivatives thereof.

The organosilicon compound represented by the general formula (1) includes a perhydroquinolino compound represented by the general formula (3), a perhydroisoquinolino compound represented by the general formula (4), (Perhydroquinolino) represented by (5) (perhydroisoquinolino compound, 1,2,3,4-tetrahydroquinolino compound represented by general formula (6), represented by general formula (7) 1,2,3,4-tetrahydroisoquinolino compound, (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compound in general formula (8) Is mentioned.

[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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[0047]

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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 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 R3 N may be one or more.

The compound represented by the general formula (3) 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, bis (6-methylperhydroquinolino) dimethoxysilane, bis (7-methylperhydroquinolino) dimethoxysilane, bis (8-methylperhydroquinolino) dimethoxysilane, bis (9-methylperhydroquinolino) dimethoxysilane And bis (methyl-substituted perhydroquinolino) dimethoxysilane, such as bis (10-methylperhydroquinolino) 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 (2,10-dimethylperhydronolino) dimethoxy Silane, bis (3,4-dimethylperhydroquinolino) dimethoxysilane, bis (3,5-dimethylperhydroquinolino) dimethoxysilane, bis (3,6-dimethylperhydroquinolino) dimethoxysilanebis (3,7-dimethyl Perhydroquinolino) dimethoxysilane, bis (3,8-dimethylperhydroquinolino) dimethoxysilane, bis (3,9-dimethylperhydroquinolino) dimethoxysilane, bis (3,10-dimethylperhydroquinolino) dimethoxysilane, bis (4,5-dimethylperhydroquinolino)
Dimethoxysilane, bis (4,6-dimethylperhydroquinolino) dimethoxysilane, bis (4,7-dimethylperhydroquinolino) dimethoxysilane, bis (4,8-dimethylperhydroquinolino) dimethoxysilane, bis (4.9-dimethyl Perhydroquinolino) dimethoxysilane, bis (4,
10-dimethylperhydroquinolino) dimethoxysilane,
Bis (5,6-dimethylperhydroquinolino) dimethoxysilane, bis (5.7-dimethylperhydroquinolino) dimethoxysilane, bis (5,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (5,9-dimethylperhydroquinolino) dimethoxysilane, bis (5,10-dimethylperhydroquinolino) dimethoxysilane, bis (6,7-dimethylperhydroquinolino) dimethoxysilane, bis (6,8 -Dimethylperhydroquinolino) dimethoxysilane, bis (6,9-dimethylperhydroquinolino) dimethoxysilane, bis (6,10-dimethylperhydroquinolino) dimethoxysilane, bis (7,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (7,9-dimethylperhydroquinolino) dimethoxysilane, bis (7,10-dimethylperhydroquinolino) dimethoxysilane, bis (8,9-dimethylperhydroquinolino) dimethoxysilane, bis (8,10 -
Bis (dimethyl-substituted perhydroquinolino) dimethoxysilane such as dimethylperhydroquinolino) dimethoxysilane and bis (9,10-dimethylperhydroquinolino) dimethoxysilane.

Further, bis (2,3,4-trimethylperhydroquinolino) dimethoxysilane, bis (3,4,5-trimethylperhydroquinolino) dimethoxysilane, bis (4,5,6-
Trimethylperhydroquinolino) dimethoxysilane, bis (5,6,7-trimethylperhydroquinolino) dimethoxysilane, bis (6,7,8-trimethylperhydroquinolino)
Bis (trimethyl-substituted perhydroquinolino) dimethoxysilane compounds such as dimethoxysilane, bis (7,8,9-trimethylperhydroquinolino) dimethoxysilane and bis (8,9,10-trimethylperhydroquinolino) dimethoxysilane; .

Also, (perhydroquinolino) (2-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (3-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (4-methylperhydroquinolino) Dimethoxysilane, (perhydroquinolino)
(5-methylperhydroquinolino) dimethoxysilane,
(Perhydroquinolino) (6-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (7-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (8-methylperhydroquinolino) dimethoxysilane, (per Compounds such as (hydroquinolino) (9-methylperhydroquinolino) dimethoxysilane and (perhydroquinolino) (10-methylperhydroquinolino) dimethoxysilane are exemplified.

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

As the compound represented by the general formula (4),
Bis (perhydroisoquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (1-methylperhydroisoquinolino) dimethoxysilane, bis (3-methylperhydroisoquinolino) dimethoxysilane, bis (4-methylperhydroisoquinolino) dimethoxysilane, bis (5 -Methylperhydroisoquinolino) dimethoxysilane, bis (6-
Methyl perhydroisoquinolino) dimethoxysilane, bis (7-methylperhydroisoquinolino) dimethoxysilane, bis (8-methylperhydroisoquinolino) dimethoxysilane, bis (9-methylperhydroisoquinolino) dimethoxy Examples include bis (methyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as silane and bis (10-methylperhydroisoquinolino) dimethoxysilane.

Further, bis (1,3-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,5-dimethylperhydroisoquinolino) Dimethoxysilane, bis (1,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,7-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (1,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,10-
Dimethyl perhydroisoquinolino) dimethoxysilane,
Bis (3,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,5-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,6-dimethylperhydroisoquinolino) dimethoxysilane, bis ( 3,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,
8-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,5- Dimethylperhydroisoquinolino) dimethoxysilane, bis (4,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,8-dimethylper) Hydroisoquinolino) dimethoxysilane, bis (4,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,6-dimethylperhydroiso) Quinolino) dimethoxysilane, bis (5,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,8-dimethylperhydro Isoquinolino)
Dimethoxysilane, bis (5,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,7-
Dimethyl perhydroisoquinolino) dimethoxysilane,
Bis (6,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,10-dimethylperhydroisoquinolino) dimethoxysilane, bis ( 7,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (7,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (7,10-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (8,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (8,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (9,10
-Bis (dimethyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as dimethylperhydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4-trimethylperhydroisoquinolino) dimethoxysilane, bis (3,4,5-trimethylperhydroisoquinolino) dimethoxysilane, bis (4,5,6-trimethyl) Perhydroisoquinolino) dimethoxysilane, bis (5,6,7-trimethylperhydroisoquinolino) dimethoxysilane, bis (6,7,8-trimethylperhydroisoquinolino) dimethoxysilane, bis (7,8 , 9-
And bis (trimethyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as trimethylperhydroisoquinolino) dimethoxysilane and bis (8,9,10-trimethylperhydroisoquinolino) dimethoxysilane.

Further, (perhydroisoquinolino) (2-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (3-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) Reno)
(4-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (6-methylperhydroisoquinolino) Dimethoxysilane, (perhydroisoquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) (8-methylperhydroisoquinolino) dimethoxysilane, (perhydroisoquinolino) Compounds such as (9-methylperhydroisoquinolino) dimethoxysilane and (perhydroisoquinolino) (10-methylperhydroisoquinolino) dimethoxysilane are exemplified.

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

The compound represented by the general formula (5) includes
(Perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (1-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (3-methylperhydroisoquinolino) dimethoxysilane , (Perhydroquinolino) (4-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (6-methylperhydroisoquino (Rino) dimethoxysilane, (perhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (8-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (9-methyl (Perhydroisoquinolino) dimethoxysilane, (perhydroxy Nolino (10-methylperhydroisoquinolino) dimethoxysilane, (2-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (3-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane , (4-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (5-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (6-methylperhydroquinolino) (perhydroisoquino (Rino) dimethoxysilane, (7-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (9-methylperhydroquinolino) ( (Perhydroisoquinolino) dimethoxysilane, (10-methylperoxide) Quinolino) (perhydroisoquinolino) dimethoxysilane, (2-methylperhydroquinolino) (1-methylperhydroisoquinolino) dimethoxysilane, (3-methylperhydroquinolino) (3-methylperhydroisoquinolino )
Dimethoxysilane, (4-methylperhydroquinolino)
(4-methylperhydroisoquinolino) dimethoxysilane, (5-methylperhydroquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (6-methylperhydroquinolino) (6-methylperhydroisoquino Reno)
Dimethoxysilane, (7-methylperhydroquinolino)
(7-methylperhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinolino) (8-methylperhydroisoquinolino) dimethoxysilane, (9-methylperhydroquinolino) (9-methylperhydroisoquino) Reno)
Dimethoxysilane, (10-methylperhydroquinolino)
Compounds such as (10-methylperhydroisoquinolino) dimethoxysilane are exemplified.

Among the above compounds, (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane is preferred.

As the compound represented by the general formula (6),
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-tetrahydroquino Lino) dimethoxysilane, bis (7-methyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (8-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (9-methyl-1,2,3,4-tetrahydroquinolino)
And bis (methyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as dimethoxysilane.

Further, bis (2,3-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and 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-1,2,3,4-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-1,2,3,4-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-1,2,3,4-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)
And bis (dimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as -1,2,3,4-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-tetrahydro Quinolino) dimethoxysilane, bis (2,3,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,9-trimethyl-1,2,3,4-tetrahydro Quinolino) 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
And bis (trimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as -1,2,3,4-tetrahydroquinolino) dimethoxysilane.

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-tetra Methyl-
1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,3,4,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,7-tetramethyl-1,2,3,4-tetrahydro Quinolino) 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 and bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane And compounds such as substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane.

Among the above compounds, bis (1,2,3,4-tetrahydroquinolino) dimethoxysilanedimethoxysilane is preferred.

Also, bis (perhydroindolino) dimethoxysilane, bis (perhydroisoindolino)
Dimethoxysilane and the like.

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

[0071]

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[0072]

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Examples of the organosilicon compound represented by the general formula (2) include a perhydroquinolino compound represented by the general formula (9) and a perhydroisoquinolino compound represented by the general formula (10). Can be

[0074]

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[0075]

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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,
Methyl group, ethyl group, n-propyl group, iso-propyl group,
Examples thereof include 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.

As the compound represented by the general formula (9),
Ethyl (perhydroquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, iso-
Propyl (perhydroquinolino) dimethoxysilane, n-
Butyl (perhydroquinolino) dimethoxysilane, iso-
Propyl (perhydroquinolino) dimethoxysilane, te
r-butyl (perhydroquinolino) dimethoxysilane, se
c-butyl (perhydroquinolino) dimethoxysilane, n-
Pentyl (perhydroquinolino) dimethoxysilane, is
o-pentyl (perhydroquinolino) dimethoxysilane,
Cyclopentyl (perhydroquinolino) dimethoxysilane, n-hexyl (perhydroquinolino) dimethoxysilane, cyclohexyl (perhydroquinolino) dimethoxysilane, texyl (perhydroquinolino) dimethoxysilane, n-octyl (perhydroquinolino) dimethoxysilane, phenyl Examples include perhydroquinolinosilane compounds such as (perhydroquinolino) dimethoxysilane, piperidino (perhydroquinolino) dimethoxysilane, and diethylamino (perhydroquinolino) dimethoxysilane.

Ethyl (2-methylperhydroquinolino) dimethoxysilane, n-propyl (2-methylperhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane, n-butyl (2-methyl Perhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane,
iso-butyl (2-methylperhydroquinolino) dimethoxysilane, ter-butyl (2-methylperhydroquinolino)
Dimethoxysilane, sec-butyl (2-methylperhydroquinolino) dimethoxysilane, n-pentyl (2-methylperhydroquinolino) dimethoxysilane, iso-pentyl (2-
Methyl perhydroquinolino) dimethoxysilacyclopentyl (2-methylperhydroquinolino) dimethoxysilane, n-hexyl (2-methylperhydroquinolino) dimethoxysilane, cyclohexyl (2-methylperhydroquinolino) dimethoxysilane, texyl (2-methyl Perhydroquinolino) dimethoxysilane, n-octyl (2-methylperhydroquinolino) dimethoxysilane, n-decyl (2-
2-methylperhydroquinolinosilane compounds such as methylperhydroquinolino) dimethoxysilane, 2-decalino (2-methylperhydroquinolino) dimethoxysilane, and phenyl (2-methylperhydroquinolino) dimethoxysilane.

Iso-propyl (3-methylperhydroquinolino) dimethoxysilane, iso-propyl (4-methylperhydroquinolino) dimethoxysilane, iso-propyl (5-methylperhydroquinolino) dimethoxysilane, iso-propyl (6 -Methylperhydroquinolino) dimethoxysilane, iso-propyl (7-methylperhydroquinolino) dimethoxysilane, iso-propyl (8-methylperhydroquinolino) dimethoxysilane, iso-propyl (9-methylperhydroquinolino) dimethoxysilane , Iso-propyl (10
-Methyl-substituted perhydroquinolinosilane compounds such as methyl perhydroquinolino) dimethoxysilane.

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

The compounds represented by the general formula (10) include ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, and iso-propyl (perhydroisoquinolino) Dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, iso-butyl (perhydroisoquinolino) dimethoxysilane, ter-butyl (perhydroisoquino) Lino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-pentyl (perhydroisoquinolino) dimethoxysilane, iso-pentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroisoquino) Lino) dimethoxysilane, n-hexyl (perhydroiso Norino) dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, thexyl (perhydroisoquinolino)
Dimethoxysilane, n-octyl (perhydroisoquinolino) dimethoxysilane, n-decyl (perhydroisoquinolino) dimethoxysilane, 2-decalino (perhydroisoquinolino) dimethoxysilane, phenyl (perhydroisoquinolino) Dimethoxysilane, piperidino (perhydroisoquinolidimethoxysilane, diethylamino (part
Perhydroisoquinolinosilane compounds such as (hydroisoquinolino) dimethoxysilane.

Ethyl (2-methylperhydroisoquinolino) dimethoxysilane, n-propyl (2-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (2-
Methyl perhydroisoquinolino) dimethoxysilane, n-
Butyl (2-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (2-methylperhydroisoquinolino) dimethoxysilane, ter-butyl (2-methylperhydroisoquinolino) dimethoxysilane, sec-butyl ( 2-methylperhydroisoquinolino) dimethoxysilane, n-pentyl (2-methylperhydroisoquinolino) dimethoxysilane, iso-pentyl (2-methylperhydroisoquinolino) dimethoxysilane, cyclopentyl (2-methylper Hydroisoquinolino) dimethoxysilane, n-hexyl (2-methylperhydroisoquinolino) dimethoxysilane, cyclohexyl (2-methylperhydroisoquinolino) dimethoxysilane, texyl (2-methylperhydroisoquinolino) dimethoxy Silane, n-octyl (2-methylperhydroisoquinolino) dimethoxy Run, phenyl (2-methyl-perhydroisoquinolino) 2-methyl-perhydro isoquinolinium aminosilane compounds such as dimethoxysilane and the like.

Further, iso-propyl (3-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (4-methylperhydroisoquinolino) dimethoxysilane,
Propyl (5-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (6-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (7-methylperhydroisoquinolino) dimethoxysilane, iso-propyl ( Methyl-substituted perhydroisoxyl such as 8-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (9-methylperhydroisoquinolidimethoxysilane, iso-propyl (10-methylperhydroisoquinolino) dimethoxysilane Norinosilane compounds are exemplified.

Among the above, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane Quinolino) dimethysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, iso-butyl (perhydroisoquinolino) dimethoxysilane ter-butyl (perhydroisoquinolinodimethoxysilane, sec-butyl (perhydroisoquino) Rino) dimethoxysilane, n-
Compounds such as hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane, and diethylamino (per-hydroisoquinolino) dimethoxysilane are preferred.

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

[0086]

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[0087]

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In the organosilicon compound having two polycyclic amino groups, a geometric 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. For example, as a specific example, a bis (trans-
Perhydroquinolino) dimethoxysilane, bis (cis-
Perhydroquinolino) dimethoxysilane, bis (trans-perhydroisoquinolino) dimethoxysilane, bis (cis-perhydroisoquinolino) dimethoxysilane and the like. These isomers may be used alone or in a mixture of isomers as the component [C] of the present invention.

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

In the present invention, the catalyst solid component [A] is previously subjected to contact treatment with the organoaluminum compound component [B] and the organosilicon compound component [C], and a pre-contact treated solid is prepared by washing the solid.

The amount of the organoaluminum compound component [B] used in the preliminary contact treatment is usually such that the molar ratio of Al / Ti to titanium atom of the solid catalyst component [A] is 1 to 50, and preferably 1 to 50.
5-20.

The amount of the organosilicon compound component [C] to be used in the preliminary contact treatment is usually such that the molar ratio of Si / Al to the aluminum atom of component [B] is 0.01 to 2, preferably 0.1 to 0.1.
~ 1.

The preliminary contact treatment method includes the components [A],
The component [B] and the component [C] are mixed and usually mixed at 0 to 70 ° C.
React for 0.1 to 10 hours. The mixing order of each component is not particularly limited, but usually, the order of component [A], component [B], and component [C] is preferable.

After the pre-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 pre-polymerization or main polymerization.

The pre-contact treatment has the effect of improving the polymerization activity and the stereoregularity of the polymer.

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 gas phase polymerization in which a monomer is brought into contact with a catalyst in a gaseous state to carry out polymerization. A bulk polymerization method in which a monomer in a liquefied state is polymerized in a solvent as a solvent can be employed. In the above polymerization method, either continuous polymerization or batch polymerization may be performed.

The polymerization pressure is from 0.1 to 20 MPa, preferably from 1 to 20 MPa.
6MPa, polymerization temperature 10 ~ 150 ° C, preferably 30 ~ 100 ° C,
Particularly preferably, it is 60 to 90 ° C. The polymerization time is usually 0.1 to
It is 10 hours, preferably in the range of 0.5 to 7 hours.

In the present invention, at the time of the main polymerization, it is preferable to carry out the polymerization by further adding the component [B] to the solid component subjected to the preliminary contact treatment. When the component [B] is used at the time of polymerization, the amount of the component [B] to be used is usually an Al / Ti molar ratio of 10 to 800, preferably 100 to 400, based on titanium atoms in the pre-contact treated solid. .

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 is usually 0.05 to 3.0 hydrogen partial pressure. Range.

In the method for polymerizing α-olefins according to the present invention, prepolymerization with ethylene or α-olefin is not necessarily required.
-It is preferable to carry out olefin main polymerization. The effect of the prepolymerization includes stabilization of the particle shape of the polymer in addition to improvement of the polymerization activity and stereoregularity of the polymer.
As the prepolymerization, a prepolymerized solid can be prepared by polymerizing a limited amount of ethylene or α-olefin in the presence of the component [B] or the component [C] using the pretreated solid.

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.

In the method for polymerizing an α-olefin according to the present invention, by adding an organosilicon compound component [C] in addition to the organoaluminum compound component [B] at the time of α-olefin main polymerization, the polymerization activity can be further improved. 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, to lower the melting point, and to increase the transparency of the film α-
In the polymerization of the olefin, it may be copolymerized with a small amount of ethylene or another α-olefin.

In order to enhance 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 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. 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 by GPC 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 a 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 there is no 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, as a blend with other plastics and elastomers, as well as a reinforcing agent for inorganic and organic fillers such as glass fiber and talc, and other crystal nuclei. Agents can be mixed and used, but are not particularly limited to automobiles,
Excellent performance as a structural material for home appliances.

[0107]

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. 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 the 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. 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 advantageous for simplifying the polymerization process and reducing the production cost.

[0108]

Embodiments of the present invention will be described below. In the examples, the “polymerization activity” is the yield (Kg) of the polymer of α-olefin per 1 g of the solid catalyst.

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

An isopentad fraction obtained by examining the microtacticity of the polymer, which is an index of the tacticity of the polymer.
(mmmm)% in Macromolecule in propylene polymer
It was calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on s 8, 687 (1975). ^{The 13} C-NMR spectrum was measured using a JEOL EX-400 device, using a TM
Based on S, the temperature was measured at 130 ° C. using an o-dichlorobenzene solvent.

The molecular weight distribution was determined by weight-average molecular weight Mw and number average obtained from GPC (150 CV type, Waters, o-dichlorobenzene solvent, column SHODEX, temperature 145 ° C., concentration 0.05 wt%) using polystyrene as a standard substance. It was evaluated by the ratio Mw / Mn of the molecular weight Mn.

Reference Example (Synthesis Method of Organosilicon Compound Component [C] Synthesis Example: Bisperhydroquinolinodimethoxysilane) A stirrer piece was placed in a 200 mL three-necked flask equipped with a dropping funnel, and a vacuum pump was used. After the inside of the flask is sufficiently purged with nitrogen, 100 mL of distilled and dehydrated n-heptane is introduced into the flask.
, 17.9 mL (0.12 mol) of decahydroquinoline was added, and in the dropping funnel, 75 mL of a 1.6 M butyllithium hexane solution was added.
(0.12 mol). While maintaining the temperature in 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 for 12 hours at room temperature to obtain a lithium salt of perhydroquinoline.

Next, a stirrer piece was placed in a flask with a glass filter (capacity: 400 mL) equipped with a dropping funnel, and the inside of the flask was sufficiently purged with nitrogen using a vacuum pump. -60 mL heptane,
9 mL (0.06 mol) of tetramethoxysilane was charged, and the above-mentioned lithium salt of perhydroquinoline was charged in the dropping funnel. At room temperature, the lithium salt of perhydroquinoline 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.
The desired product, bisperhydroquinolinodimethoxysilane, was obtained. This compound had a boiling point of 189.5 ° C./3 mmHg and a GC purity of 96.5%.

Example 1 (1) Preparation of Catalyst Solid Component [A] 15 mmol of anhydrous aluminum chloride was added to 40 mL of toluene.
Next, 15 mmol of methyltriethoxysilane was added dropwise with stirring, and after the completion of the addition, the mixture was reacted at 25 ° C. for 1 hour. After cooling the reaction product to −5 ° C., 30 mL of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added under stirring.
The reaction solution is dropped at -5 to 0 ° C
Kept within the range. 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 suspended in 30 mL of toluene, and titanium tetrachloride 15
0 mmol and 3.3 mmol of di-n-heptyl phthalate were added 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, and titanium tetrachloride 150
mmol was added and reacted at 90 ° C. for 1 hour with stirring. 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 is 3.
55 wt%.

(2) Pre-contact treatment Next, under a nitrogen atmosphere, 250 mL of dehydrated and distilled n-heptane, 3.25 mmol of triethylaluminum, 3.25 mmol of bis (perhydroquinolino) were placed in a flask equipped with a glass filter (capacity: 400 mL) equipped with a stirrer. After adding 0.55 mmol of dimethoxysilane and 0.65 mmol of the above-mentioned catalyst solid component [A] in terms of titanium atom, the mixture was stirred and mixed at 10 ° C. for 60 minutes, and then filtered through a glass filter. After washing the pretreated catalyst solid obtained with 100 mL of dehydrated / distilled n-heptane twice, 100 mL of dehydrated / distilled n-heptane was added again to form a slurry.

(3) Propylene Polymerization In a 2 L stainless steel autoclave equipped with a stirrer, 0.005 mmol of the n-heptane slurry of the pretreated catalyst solid component obtained above in terms of titanium atom and the organoaluminum compound component [B ] As triethyl aluminum 2.
1 mmol, then 0.2 MPa hydrogen, liquefied propylene 1.2 L
Was introduced. The temperature in the autoclave was raised, the internal temperature was kept at 70 ° C, and polymerization was carried out for 1 hour. After completion of the polymerization, unreacted propylene gas is released, and the polymer is dried under reduced pressure at 50 ° C for 20 hours.
A white powdery polypropylene was obtained. Polymerization activity was 39.3
Kg-PP / g-Cat.h, MFR = 34.3, mmmm = 96.6%, Mw /
Mn = 17.8.

Example 2 Pretreatment Catalyst Bis (perhydroquinolino)
The procedure was performed in the same manner as in Example 1 except that bis (perhydroisoquinolino) dimethoxysilane was used instead of dimethoxysilane. As a result, the polymerization activity was 40.1Kg-PP / g-
Cat.h, MFR = 17.8, mmmm = 96.7%, Mw / Mn = 1
It was 8.8.

Example 3 Pretreatment Catalyst Bis (perhydroquinolino)
The procedure was performed in the same manner as in Example 1 except that iso-butyl (perhydroisoquinolino) dimethoxysilane was used instead of dimethoxysilane. As a result, the polymerization activity was 43.3 kg
-PP / g-Cat.h, MFR = 35.5, mmmm = 97.0%, Mw / M
n = 11.2.

COMPARATIVE EXAMPLE 1 Bis (perhydroquinolino)
The procedure was performed in the same manner as in Example 1 except that dimethoxysilane was not used. As a result, the polymerization activity is 29.7Kg-PP / g-Ca
th, MFR = 181, mmmm = 80.4%, Mw / Mn = 8.7
Met.

Comparative Example 2 Bis (perhydroquinolino)
Cyclohexyl (methyl) instead of dimethoxysilane
The procedure was performed in the same manner as in Example 1 except that dimethoxysilane was used. As a result, the polymerization activity was 39.8 Kg-PP / g-Cat.h,
MFR = 74.2, mmmm = 93.2%, Mw / Mn = 6.9.

[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.

Claims (1)

[Claims] 1. A component represented by the following general formula (1) or (2): [A] a catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] a general formula (1) or (2). A polymerization method for an α-olefin, characterized in that the α-olefin is polymerized or copolymerized in the presence of a catalyst obtained by pre-contacting the organosilicon compound component. Embedded image 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.
And R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom. )