JP2001106717A - Method for polymerizing alpha-olefin and alpha-olefin polymer produced by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly active α-olefin polymer having high stereoregularity and a wide mol.wt. distribution. SOLUTION: This method for polymerizing an α-olefin comprises adding [A] a catalyst solid component consisting essentially of magnesium, titanium, a halogen element and an electron donor, [B] an organic aluminum compound component, and [C] a specific polycyclic amino-containing organic silicon compound component, and polymerizing or copolymerizing the α-olefin. Therein, the [A] catalyst solid component is preliminarily treated in the presence of a halogen-containing organic aluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pretreatment in the presence of a halogen-containing organoaluminum, followed by a main polymerization in the presence of an organoaluminum compound containing no halogen atom and an organosilicon compound having a specific structure. A method for producing a homopolymer of an α-olefin having a high activity, a high stereoregularity, and a wide molecular weight distribution, or a copolymer with another α-olefin, and an α-olefin polymer obtained by the method It is about coalescence.

[0002]

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

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

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

Japanese Patent Application Laid-Open Nos. 6-25336, 7-90012, and 7-97411 disclose nitrogen in which an arbitrary carbon atom in a heterocyclic ring is directly bonded to a silicon atom. A method using an atom-containing heterocyclic-substituted organosilicon compound is disclosed, but the molecular weight distribution is not described. 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 stereoregularity is obtained by separating a low-molecular-weight propylene polymer having high stereoregularity and a high-molecular-weight propylene polymer having high stereoregularity by a conventional method. Manufactured in
A method of melting and mixing them at a desired ratio can be considered.
However, particularly when the difference in molecular weight between the low-molecular-weight propylene polymer and the high-molecular-weight propylene polymer is large, it is extremely difficult to uniformly melt and mix, and problems such as gel formation and reduced impact resistance occur.

[0007] Japanese Patent Application Laid-Open No. 10-218926 and the like disclose:
By using an organosilicon compound having a polycyclic amino group, a method of obtaining an α-olefin polymer having high stereoregularity and a wide molecular weight distribution is disclosed, but a conventional organosilicon compound was used. There was a problem that the polymerization activity was lower than in the case.

[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]

Means for Solving the Problems [A] A catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, [C] a general formula (1) or (2) An α-olefin is polymerized or copolymerized by adding an organosilicon compound component represented by
-A method for polymerizing an α-olefin, characterized in that the solid catalyst component is pretreated in the presence of an organoaluminum containing halogen in the method for polymerizing an olefin, and an α-olefin polymer produced by the method.

[0010]

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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. )

Further, in the present invention, the pretreatment of the solid catalyst component [A] is preferably to prepolymerize an α-olefin in the presence of a halogen-containing organoaluminum compound. For the polymerization of α-olefins.

The present invention is also characterized in that the pretreatment of the solid catalyst component (A) is carried out in the presence of a mixture of a halogen-containing organic aluminum compound and a halogen-free organic aluminum compound. 3. A method for polymerizing an α-olefin according to 1 or 2.

Further, the present invention relates to the method for polymerizing α-olefins according to any one of claims 1 to 3, wherein an organic silicon compound is further added in the pretreatment of the solid catalyst component (A). .

The present invention also relates to a ratio (Mw / Mn value) between the weight average molecular weight Mw and the number average molecular weight Mn of the α-olefin polymer produced by the above polymerization method, as determined by GPC measurement in terms of polystyrene. Is 8 to 25, and relates to the method for polymerizing an α-olefin according to any one of claims 1 to 4.

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

[0017]

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

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

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

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

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

Specific examples of the magnesium compound used in the above reaction include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, propyl magnesium bromide, butyl magnesium bromide, 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 to be used is usually 0.5 to 3, preferably 1, in terms of an element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound. 5-
The range is 2.3. The reaction temperature is usually -50 to 100
℃, preferably -20 to 50 ℃, the reaction time is usually 0.2
-5 hours, preferably 0.5-3 hours.

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

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

Specific examples of titanium halide compounds 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-ethylhexyl orthophthalate.
n-Heptyl, di-n-octyl orthophthalate and the like.

Further, as an electron donor, JP-A-3-70
No. 6, No. 3-62805, No. 4-27070
No. 5, JP-A-6-25332 may be used. For example, 2,2-
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 , 3-Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-
Cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,
3-dimethoxypropane and the like.

After the above-mentioned contact treatment, the treated solid is generally separated from the treated mixture, and the solid obtained by sufficiently washing with an inert solvent is obtained as the catalyst solid component [A] of the present invention.

In the present invention, the catalyst solid component [A] obtained above is pretreated before the main polymerization. As a method of performing the preliminary treatment, there is the following method. Here, the pretreatment means precontact or prepolymerization. (1) A method in which the catalyst solid component [A] is pre-contacted with a halogen-containing organoaluminum compound. (2) A method in which the catalyst solid component [A] is pre-contacted with a mixture of a halogen-containing organoaluminum compound and a halogen-free organoaluminum compound. (3) A method of prepolymerizing an α-olefin in the presence of a catalyst-containing solid component [A] in the presence of a halogen-containing organoaluminum compound. (4) A method in which the catalyst solid component [A] is prepolymerized with an α-olefin in the presence of a mixture of a halogen-containing organoaluminum compound and a halogen-free organoaluminum compound. (5) The method of (1) to (4), wherein an organosilicon compound is further added.

In the pretreatment, the amount of the halogen-containing organoaluminum compound used is 1: 0.000 as a molar ratio of titanium to aluminum (Ti: Al) in the catalyst solid component.
It is preferably from 5 to 1:30, particularly preferably from 1: 1 to 1:10.

When a mixture of a halogen-containing organoaluminum compound and an organoaluminum compound containing no halogen atom is used in the pretreatment, the molar ratio thereof is as follows:
(Halogen-containing organoaluminum compound): (organoaluminum compound not containing a halogen atom) = 1: 0.1
１ ： 1: 5 is preferred. In particular, 1: 0.5 to 1: 1.5 is preferable.

When an organic silicon compound is further added in the pretreatment, the molar ratio of titanium to silicon (Ti: Si) in the catalyst solid component is preferably from 1: 0.01 to 1:10. Also, the molar ratio of aluminum to silicon (Al:
As Si), 1: 0.01 to 1: 2 is preferable.

When an organic silicon compound is further added in the pretreatment, the above-mentioned organic silicon compound represented by the general formula (1) or (2) is preferred.

When the pretreatment is a method in which the catalyst solid component [A] is prepolymerized with an α-olefin, the prepolymerization ratio is defined as 0.1 mass of prepolymer / component [A] (weight ratio).
It is from 01 to 1000, preferably from 0.1 to 20. The effects of pre-polymerization include the improvement of polymerization activity and the stereoregularity of the polymer, as well as the particle shape (morphology) of the polymer.
Stabilization.

The pretreatment in the present invention can be performed by a gas phase method, a slurry method, a bulk method, or the like. The solid obtained in the pretreatment may be separated and then used for the main polymerization, or the main polymerization may be carried out without separation.

As the organoaluminum compound component [B] of the present invention, an organoaluminum compound containing no halogen atom and a halogen-containing organoaluminum compound can be used. Specific examples of the organoaluminum compound containing no halogen atom include trimethylaluminum,
Triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, trin-butylaluminum, trin-hexylaluminum, trin-
Octyl aluminum and tri-n-decyl aluminum are exemplified. Specific examples of the halogen-containing organic aluminum compound include methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, diethyl aluminum chloride, di-n
-Propylaluminum chloride, diisobutylaluminum chloride and the like. Any of the above-mentioned organoaluminum compounds can be used as a mixture. Of these, diethyl aluminum chloride and triethyl aluminum are particularly preferred.

In the present polymerization, the component [C] is added with an organosilicon compound component represented by the general formula (1) or (2) to add α.
Polymerizing or copolymerizing olefins.

[0039]

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[0040]

Embedded image (However, in (1) or (2), R ¹ has ¹ carbon atom.
Represents a hydrocarbon group having from 8 to 8, R ² represents a hydrocarbon group having ^{2 to} 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or a hydrocarbon alkoxy group having 1 to 24 carbon atoms, and R ³ N represents It represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton 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,
n-propyl group, iso-propyl group, n-butyl group,
iso-butyl group, ter-butyl group, sec-butyl group, n-pentyl group, 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 having 2 to 24, preferably 2 to 8 carbon atoms, or a hydrocarbon alkoxy group having 1 to 24, preferably 1 to 8 carbon atoms. Among them, a hydrocarbon group having 2 to 24 carbon atoms or a hydrocarbon amino group having 2 to 24 carbon atoms is exemplified.

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, te
r-butyl group, n-pentyl group, isopentyl group, n-
Examples include a hexyl group, an n-heptyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, a texyl group, a phenyl group, a benzyl group, and a toluyl group. 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-
Propyl group such as propyl group, iso-butyl group, te
A butyl group such as an r-butyl group, a cyclopentyl group, a diethylamino group, a ter-butoxy group and the like are suitably 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 (Si-N bond). 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 a specific example of R ³ NH, as shown by the following chemical structural formula,

[0048]

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Perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroacridine,
Perhydrophenanthridine, perhydrobenzo (g)
Quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline,
Amine compounds such as hydrobenzo (f) isoquinoline, perhydroacequinoline, perhydroaceisoquinoline, and perhydroiminostilbene; and further, in the above amine compounds, a part of hydrogen atoms other than nitrogen atoms is an alkyl group or a phenyl group. And an amine compound substituted with a cycloalkyl group.

Further, R ³ NH is represented by the following chemical structural formula:

[0051]

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

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

Examples of the organosilicon compound represented by the general formula (1) include a bis (perhydroquinolino) compound represented by the general formula (3) and a bis (perhydrohydrolino) compound represented by the general formula (4). A quinolino) compound, a (per-hydroquinolino) compound represented by the general formula (5) (a perhydroisoquinoli compound, a bis (1,2,3,4-tetrahydroquinolino) compound represented by the general formula (6)) Bis (1,2,3,4-tetrahydroisoquinolino) compound represented by the general formula (7), and (1,2,3,4-tetrahydroquinolino) (1,2,2) 3,4-tetrahydroisoquinolino) compound.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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

As the compound represented by the general formula (3),
Bis (perhydroquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (2-methylpa-hydroquinolino) dimethoxysilane, bis (3-methylpa-hydroquinolino) dimethoxysilane, bis (4-methylpa-hydroquinolino) dimethoxysilane, bis (5-methylpa-
(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-dimethylperhydronorino) dimethoxysilane, bis (3,4-dimethylperhydroquinolino) dimethoxysilane, bis (3,5-dimethylperhydroquinolino)
Dimethoxysilane, bis (3,6-dimethylperhydroquinolino) dimethoxysilanebis (3,7-dimethylperhydroquinolino) dimethoxysilane, bis (3,8-
Dimethyl per-hydroquinolino) dimethoxysilane, bis (3,9-dimethyl per-hydroquinolino) dimethoxysilane, bis (3,10-dimethyl per-hydroquinolino)
Dimethoxysilane, bis (4,5-dimethylperhydroquinolino) dimethoxysilane, bis (4,6-dimethylperhydroquinolino) dimethoxysilane, bis (4,7
-Dimethylperhydroquinolino) dimethoxysilane, bis (4,8-dimethylperhydroquinolino) dimethoxysilane, bis (4.9-dimethylperhydroquinolino)
Dimethoxysilane, bis (4,10-dimethylperhydroquinolino) dimethoxysilane, bis (5,6-dimethylperhydroquinolino) dimethoxysilane, bis (5.
7-dimethylper-hydroquinolino) dimethoxysilane,
Bis (5,8-dimethylper-hydroquinolino) dimethoxysilane, bis (5,9-dimethylper-hydroquinolino) dimethoxysilane, bis (5,10-dimethylpar-
(Hydroquinolino) dimethoxysilane, bis (6,7-dimethylperhydroquinolino) dimethoxysilane, bis (6,8-dimethylperhydroquinolino) dimethoxysilane, bis (6,9-dimethylperhydroquinolino) dimethoxysilane, bis (6,10- Dimethylper-hydroquinolino) dimethoxysilane, bis (7,8-dimethylper-hydroquinolino) dimethoxysilane, bis (7,9
-Dimethylper-hydroquinolino) dimethoxysilane, bis (7,10-dimethylper-hydroquinolino) dimethoxysilane, bis (8,9-dimethylper-hydroquinolino) dimethoxysilane, bis (8,10-dimethylpar-
Hydroquinolino) dimethoxysilane, bis (9,10-
Bis (dimethyl-substituted per-hydroquinolino) dimethoxysilane such as 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 (4),
Bis (perhydroisoquinolino) dimethoxysilane; and the like.

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

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

Further, bis (1,3,4-trimethylpar-
Hydroisoquinolino) dimethoxysilane, bis (3,
4,5-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (4,5,6-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (5,6,7-trimethylpa-hydroisoquinolino) Dimethoxysilane,
Bis (6,7,8-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (7,8,9-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (8,9,10-trimethylpa-hydro) 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 (5) 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-methylpa-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) ) (Perhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinolino)
(Perhydroisoquinolino) dimethoxysilane, (9-
Methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (10-methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane,
(2-methylpa-hydroquinolino) (1-methylpa-hydroisoquinolino) dimethoxysilane, (3-methylpa-hydroquinolino) (3-methylpa-hydroisoquinolino) dimethoxysilane, (4-methylpa-hydroquinolino) (4- (5-methylperhydroisoquinolino) dimethoxysilane, (5-methylperhydroisoquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (6-
Methyl per-hydroquinolino (6-methyl per-hydroisoquinolino) dimethoxysilane, (7-methyl per-hydroquinolino) (7-methyl per-hydroisoquinolino) dimethoxysilane, (8-methyl per-hydroquinolino)
(8-methylpa-hydroisoquinolino) dimethoxysilane, (9-methylpa-hydroquinolino) (9-methylpa-hydroisoquinolino) dimethoxysilane, (10-methylpa-hydroquinolino) (10-methylpa-hydroisoquinolino) Examples include compounds such as dimethoxysilane.

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

The compound represented by the general formula (6) includes
Bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like can be mentioned.

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

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

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

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

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

Particularly preferred among the compounds represented by the general formula (7) is bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane.

Particularly preferred among the compounds represented by the general formula (8) are (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane It is.

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

[0085]

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[0086]

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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 perhydrohydroquinolino compound represented by the general formula (10). No.

[0088]

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[0089]

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R ⁴ represents a substituent on the saturated ring of R ³ N, and is hydrogen or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred as R ⁴ is hydrogen, methyl, ethyl, n- propyl, iso- propyl, n- butyl, iso- butyl group, ter-butyl group, etc. sec- butyl group. In addition, R ³ N
May have one or more hydrocarbon substituents on the saturated ring.

The compound represented by the general formula (9) includes
Ethyl (perhydroquinolino) dimethoxysilane, n-
Propyl (perhydroquinolino) dimethoxysilane, i
So-propyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, iso-butyl (perhydroquinolino) dimethoxysilane, ter-butyl (perhydroquinolino) dimethoxysilane, sec-butyl (per- Hydroquinolino) dimethoxysilane, n-pentyl (perhydroquinolino)
Dimethoxysilane, iso-pentyl (perhydroquinolino) dimethoxysilane, cyclopentyl (perhydroquinolino) dimethoxysilane, n-hexyl (perhydroquinolino) dimethoxysilane, cyclohexyl (per-
(Hydroquinolino) dimethoxysilane, texil (perhydroquinolino) dimethoxysilane, n-octyl (part
Hydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, diethylamino (per-hydroquinolino) dimethoxysilane, iso-propoxy (per-hydroquinolino) dimethoxysilane, ter
Perhydroquinolinosilane compounds such as -butoxy (perhydroquinolino) dimethoxysilane.

Ethyl (2-methylperhydroquinolino)
Dimethoxysilane, n-propyl (2-methylper-hydroquinolino) dimethoxysilane, iso-propyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Butyl (2-methylperhydroquinolino) dimethoxysilane, iso-butyl (2-methylperhydroquinolino) dimethoxysilane, ter-butyl (2-methylperhydroquinolino) dimethoxysilane, sec-butyl (2-methylperhydroquinolino) dimethoxysilane,
n-pentyl (2-methylpa-hydroquinolino) dimethoxysilane, iso-pentyl (2-methylpa-hydroquinolino) dimethoxysilacyclopentyl (2-methylpa-hydroquinolino) dimethoxysilane, n-hexyl (2-methylpa-hydroquinolino) dimethoxysilane,
Cyclohexyl (2-methylperhydroquinolino) dimethoxysilane, texyl (2-methylperhydroquinolino) dimethoxysilane, n-octyl (2-methylpar-
Hydroquinolino) dimethoxysilane, n-decyl (2
-Methylper-hydroquinolino) dimethoxysilane, 2-
Examples include 2-methylperhydroquinolinosilane compounds such as decalino (2-methylperhydroquinolino) dimethoxysilane and phenyl (2-methylperhydroquinolino) dimethoxysilane.

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 per-hydroquinolinosilane compounds such as propyl (8-methylper-hydroquinolino) dimethoxysilane, iso-propyl (9-methylper-hydroquinolino) dimethoxysilane, and iso-propyl (10-methylper-hydroquinolino) 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, s
ec-butyl (per-hydroquinolino) dimethoxysilane, cyclopentyl (perhydroquinolino) dimethoxysilane, n-hexyl (per-hydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, diethylamino (per-hydroquinolino) dimethoxysilalane, Compounds such as ter-butoxy (perhydroquinolino) dimethoxysilane are preferred.

The compounds represented by the general formula (10) include ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroiso Quinolino) dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, iso-butyl (perhydroisoquinolino) dimethoxysilane, ter
-Butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-pentyl (perhydroisoquinolino)
Dimethoxysilane, iso-pentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroisoquinolino) dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, cyclohexyl (perhydroisoquino) (Rino) dimethoxysilane, texil (perhydroisoquinolino) dimethoxysilane, n-octyl (perhydroisoquinolino) dimethoxysilane, n-decyl (per-hydroisoquinolino) dimethoxysilane, 2-decalino (pa -Hydroisoquinolino) dimethoxysilane, phenyl (perhydroisoquinolino) dimethoxysilane, piperidino (per-hydroisoquinolidimethoxysilane), diethylamino (per-hydroisoquinolino) dimethoxysilane, iso-propoxy (par- Hydroisoquino Roh) dimethoxysilane, ter
Perhydroisoquinolinosilane compounds such as -butoxy (perhydroisoquinolino) dimethoxysilane.

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-
Methyl per-hydroisoquinolino) dimethoxysilane, cyclohexyl (2-methyl per-hydroisoquinolino) dimethoxysilane, texyl (2-methyl per-hydroisoquinolino) dimethoxysilane, n-octyl (2-methyl per-hydroisoquinolino) ) Dimethoxysilane and phenyl (2-methylperhydroisoquinolino) dimethoxysilane.

Further, iso-propyl (3-methyl-
(Hydroisoquinolino) dimethoxysilane, iso-propyl (4-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (5-methylperhydroisoquinolino) dimethoxysilane, iso-propyl (6-
Methyl per-hydroisoquinolino) dimethoxysilane, i
so-propyl (7-methylperhydroisoquinolino)
Dimethoxysilane, iso-propyl (8-methyl
Methyl-substituted perhydroisoquinolinosilane compounds such as hydroisoquinolino) dimethoxysilane, iso-propyl (9-methylperhydroisoquinolidimethoxysilane, iso-propyl (10-methylperhydroisoquinolino) dimethoxysilane Is mentioned.

Among the above, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, n-butyl (per Hydroisoquinolino) dimethysilane, iso
-Propyl (perhydroisoquinolino) dimethoxysilane, iso-butyl (perhydroisoquinolino) dimethoxysilane, ter-butyl (perhydroisoquinolininodimethoxysilane, sec-butyl (perhydroisoquinolino) ) Dimethoxysilane, cyclopentyl (perhydroisoquinolino) dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane, ter
-Butoxy (per-hydroisoquinolino) dimethoxysilane Compounds such as 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.

[0100]

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[0101]

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In the above-mentioned organosilicon compound having two saturated polycyclic amino groups, a geometrical isomer, that is, a cis-form and a trans-form exists in the portion of the saturated polycyclic amino group, and thus the (trans-multi-form) Cyclic amino) (trans-polycyclic amino) dialkoxysila (cis-polycyclic amino) (cis-polycyclic amino) dialkoxysilane, (trans-
Polycyclic amino) (cis-polycyclic amino) dialkoxysilanes are present. As a specific example, a screw (trans-
Hydroquinolino) dimethoxysilane, bis (cis-per-)
Hydroquinolino) 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) includes, for example, tetramethoxysilane, H
It can be synthesized by reacting the NR secondary amine with two equivalents of a magnesium or lithium salt. The component [D] represented by the general formula (2) can be synthesized by an equivalent reaction between an alkyltrimethoxysilane and a magnesium or lithium salt of an HNR secondary amine.

The amount of the component [C] used in the main polymerization is determined by the molar ratio of silane to aluminum (Si
/ Al) is preferably 0.01 to 2.0, and particularly preferably 0.05 to 0.5.

As the present polymerization method in the present invention, a slurry polymerization method using a non-polar solvent such as propane, butane, pentane, hexane, heptane, octane, or the like, polymerization is carried out by bringing a monomer into contact with a catalyst in a gaseous state. Gas phase polymerization,
Alternatively, 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 present polymerization method, either continuous polymerization or batch polymerization may be performed.

The polymerization pressure is usually 0.1 to 20 MPa, preferably 1 to 6 MPa, and the polymerization temperature is usually 10 to 150 ° C.
Preferably 30 to 100 ° C, particularly preferably 60 to 90
° C. The polymerization time is usually in the range of 0.1 to 10 hours, preferably 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 adding the organoaluminum compound component [B]. Organic aluminum compound component [B] during main polymerization
When the component [B] is used, the molar ratio of Al / Ti to titanium atom of the solid catalyst component [A] is 10 to 10.
It is 1000, preferably 100-600.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used for producing the α-olefin polymer having a desired molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions.

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

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

The catalyst system of the present invention has high catalytic activity,
Moreover, the obtained α-olefin polymer has high stereoregularity and wide molecular weight distribution. The molecular weight distribution was determined by weight average molecular weight M obtained by GPC measurement in terms of polystyrene.
The ratio (Mw / Mn value) of w to the number average molecular weight Mn is 8 to 2.
5, Z average molecular weight Mz and weight average molecular weight Mw
(Mz / Mw value) is preferably 5 or more.

The α-olefin polymer obtained in the present invention has a high melt viscoelasticity due to its wide molecular weight distribution, and is particularly excellent in film-forming properties such as a film. There is no typical problem of poor appearance. 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, and as a reinforcing agent for inorganic or organic fillers such as glass fiber and talc, and other crystal nuclei. Agents can be mixed and used, but are not particularly limited, and can exhibit excellent performance as structural materials for automobiles, home appliances, and the like.

[0113]

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

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

[0115]

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

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

The isopentad fraction (mmm) obtained by examining the microtacticity, which is an index of the tacticity of the polymer, was measured.
m)% is Macromol in propylene polymer
calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Eucules 8,687 (1975). ^{The 13} C-NMR spectrum is EX-40 manufactured by JEOL Ltd.
The measurement was performed using an apparatus of 0, a temperature of 130 ° C., a number of scans of 8000, and an o-dichlorobenzene solvent based on TMS.

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

Example 1 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride was added to 40 mL of toluene.
And then add methyltriethoxysilane 15 mm
ol was added dropwise with stirring, and after completion of the addition, the mixture was reacted at 25 ° C. for 1 hour. After cooling the reaction product to −5 ° C., 18 mL of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, and the temperature of the reaction solution was within the range of −5 to 0 ° C. Kept.
After completion of the dropwise addition, the temperature was gradually raised, and the reaction was continued at 30 ° C. for 1 hour. The precipitated solid was separated by filtration and washed with toluene and n-heptane. Next, 4.9 g of the obtained solid was added to toluene 3
0 mL, and the suspension is added with titanium tetrachloride 150 m
mol, 3.3 mmol of di-n-heptyl phthalate, and reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off and washed with toluene and then with n-heptane. Further, the solid was suspended again in 30 mL of toluene,
Add 150 mmol of titanium tetrachloride and stir at 90 ° C
For 1 hour. At the same temperature, the solid was filtered off, and the solid was washed with toluene and then with n-heptane. The titanium content in the obtained solid catalyst component was 3.55 wt%.

(2) Preliminary polymerization In a flask having an internal volume of 200 mL equipped with a stirrer, 100 mL of distilled and dehydrated n-heptane, and 1.2 m of diethylaluminum chloride as the organoaluminum compound component [B] were used.
mol, bis (perhydroisoquinolino) dimethoxysilane 0.2 mmol as organosilicon compound component [C]
, And then the catalyst solid component [A] obtained above was injected.
Of n-heptane slurry of 0.3957 in terms of Ti atom
mmol (component [A] / component [B] / component [C]
(Molar ratio = 1/3 / 0.5) and aged at 23 ° C for 10 minutes. Thereafter, propylene gas was continuously fed into the flask at a flow rate of 100 mL / min at normal pressure to perform preliminary polymerization for 5 minutes.

(3) Polymerization of Propylene In a 2 L stainless steel autoclave equipped with a stirrer, 0.005 mmol of the n-heptane slurry of the prepolymerized catalyst solid component obtained above in terms of titanium atom was added. 2.2 mmol of triethylaluminum was added as the organoaluminum compound component [B], and 0.36 mmol of bis (perhydroisoquinolino) dimethoxysilane was added as the organosilicon compound component [C].
Hydrogen of Pa and 1.2 L of liquefied propylene were introduced. Raise the temperature of the autoclave to 70 ° C and maintain the internal temperature at 70 ° C.
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 60 ° C. for 20 hours to obtain a white powdery polypropylene. Tables 1 and 2 show the results.
It was shown to.

Example 2 The same procedure as in Example 1 was carried out except that 0.6 mmol of diethylaluminum chloride and 0.6 mmol of triethylaluminum were used instead of 0.6 mmol of diethylaluminum chloride as the organoaluminum compound component [B] during the prepolymerization. Was. The results are shown in Tables 1 and 2.

Example 3 Bis (perhydroisoquinolino) dimethoxysilane 0.2 m was used as the organosilicon compound component [C] during the prepolymerization.
The procedure was performed in the same manner as in Example 1 except that mol was not used. The results are shown in Tables 1 and 2.

Comparative Example 1 The procedure of Example 1 was repeated except that 1.2 mmol of triethylaluminum was used instead of 1.2 mmol of diethylaluminum chloride as the organoaluminum compound component [B] during the prepolymerization. The results are shown in Tables 1 and 2.

Comparative Example 2 At the time of prepolymerization, 1.2 mmol of triethylaluminum was added as the organoaluminum compound component [B] instead of 1.2 mmol of diethylaluminum chloride, and bis (perhydroisoquinolino) was used as the organosilicon compound component [C]. The same operation as in Example 1 was performed except that 0.2 mmol of dimethoxysilane was not used. The results are shown in Tables 1 and 2.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

[Brief description of the drawings]

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

Continued on the front page F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A BA02A BA02B BB01A BB01B BC06A BC15B BC16A BC17A BC19A BC39A BC39B CA18A CA27A CA44A CB91A CB92A DA02 DA03 DA04 DA08 FA04 EB01 FA04 AA00P AA03P AA04P AA16P AA17P AA19P CA01 CA04 DA04 FA09 FA43

Claims (6)

[Claims] 1. A catalyst solid component essentially comprising [A] magnesium, titanium, a halogen element and an electron donor; [B] an organoaluminum compound component; [C] represented by the general formula (1) or (2). Α-
An α-olefin polymerization method for polymerizing or copolymerizing an olefin, wherein the catalyst solid component (A) is pretreated in the presence of a halogen-containing organoaluminum. Embedded image Embedded image (However, in (1) or (2), R ¹ has ¹ carbon atom.
Represents a hydrocarbon group having from 8 to 8, R ² represents a hydrocarbon group having ^{2 to} 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or a hydrocarbon alkoxy group having 1 to 24 carbon atoms, and R ³ N represents It represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom. ) 2. The α-olefin according to claim 1, wherein the pretreatment of the solid catalyst component [A] is to prepolymerize the α-olefin in the presence of a halogen-containing organoaluminum compound. Polymerization method. 3. The method according to claim 1, wherein the pretreatment of the solid component [A] is carried out in the presence of a mixture of a halogen-containing organic aluminum compound and a halogen-free organic aluminum compound. Α described
-A method for polymerizing olefins. 4. The α-olefin polymerization method according to claim 1, wherein an organic silicon compound is further added in the preliminary treatment of the solid catalyst component [A]. 5. A ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn of the α-olefin polymer produced by the polymerization method according to any one of claims 1 to 4 in terms of polystyrene by GPC measurement. Value) is 8-25, The polymerization method of (alpha) -olefin of Claim 1-4 characterized by the above-mentioned. 6. An α-olefin polymer produced by the method for polymerizing α-olefin according to claim 1.