JPH11322830A - Polymerization of alpha-olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an α-olefin polymer having high activity, high susceptibility to hydrogen, high stereoregularity and broad molecular weight distribution, by preliminarily polymerizing an α-olefin in the presence of a catalyst comprising a specific catalytic solid ingredient, an organic aluminum compound and an organic silicone compound and then polymerizing the α-olefin through further addition of the organic silicone compound. SOLUTION: This α-olefin polymer is obtained by preliminarily polymerizing an α-olefin in the presence of a catalyst comprising (A) a catalytic solid ingredient essentially comprising Mg, Ti, a halogen element and an electron donor, (B) an organic aluminum compound ingredient (e.g. trimethylaluminum) and (C) an organic silicone compound of formula I [wherein, R is a 1-8C hydrocarbon or the like], e.g. bis(diethylamino)dimethoxysilane and then by adding an organic silicone compound of formula II and/or formula III (wherein, R<1> is a 1-8C hydrocarbon; R<2> is a 2-24C hydrocarbon or a 2-24C hydrocarbonamino or the like; R<3> N is a 7-40C polycyclic amino) to further (co)polymerize the α-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel catalyst comprising a prepolymerization and a main polymerization using an organosilicon compound having a specific structure as a novel catalyst component, thereby having high hydrogen sensitivity, high activity and high activity. Stereoregularity and homopolymer of α-olefin having a wide molecular weight distribution, or other α-olefins
The present invention relates to a method for producing a copolymer with an olefin.

[0002]

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

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

Further, JP-A-3-7703, JP-A-4-136006 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. Is disclosed. However, 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. Operation becomes more complicated.

[0005] Japanese Patent Application Laid-Open Nos. 8-1220021, 8-143621, 8-231636
In Japanese Patent Application Laid-Open Publication No. H11-163, a method using a cyclic aminosilane compound is disclosed, but there is a problem that the molecular weight distribution is not necessarily wide in these specifically described compounds.

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

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

[0008] It is also important that the hydrogen sensitivity is high. That is, when hydrogen is present in the polymerization system to adjust the molecular weight, if the hydrogen sensitivity is low, a large amount of hydrogen is required. A polymer having a high molecular weight must be produced, and in a polymerization vessel having a pressure resistance limit, the polymerization temperature must be lowered, which has a problem of adversely affecting the production rate.

[0009]

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

[0010]

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) The organosilicon compound component represented by)

[0011]

Embedded image (Where R represents a hydrocarbon group having 1 to 8 carbon atoms). The α-olefin is prepolymerized with a catalyst comprising
The present invention relates to a method for polymerizing an α-olefin, which comprises adding an organosilicon compound represented by the general formula (2) or (3) to polymerize or copolymerize an α-olefin.

[0012]

Embedded image

[0013]

Embedded image (However, in (2) or (3), 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. )

[0014]

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

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

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

After the above-mentioned contact treatment, the solid obtained by separating the treated solid from the treated mixture and thoroughly washing it with an inert solvent is generally used as the catalyst solid component [A] of the present invention to obtain an α-olefin polymerization catalyst. Can be used as

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

The amount of the organoaluminum compound component [B] used as a polymerization catalyst for α-olefin is 0.1% in elemental ratio (Al / Ti) to titanium of the solid catalyst component [A].
It is 1-500, preferably 0.5-150.

In the present invention, in addition to the above [A] and [B], [C] an organosilicon compound component represented by the general formula (1)

[0029]

Embedded image (Where R represents a hydrocarbon group having 1 to 8 carbon atoms).

Component [C] is an organosilicon compound having a hydrocarbon amino group as represented by the general formula (1).

R is a hydrocarbon group having 1 to 8 carbon atoms, such as an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. R in the general formula (1) may be the same or different. Specific examples of R include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, ter-butyl, sec-butyl, n-pentyl, iso- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group. Particularly preferably, a methyl group,
It is an ethyl group.

As specific compounds, bis (dimethylamino) dimethoxysilane, bis (methylethylamino) dimethoxysilane, bis (diethylamino) dimethoxysilane, dimethylamino (diethylamino) dimethoxysilane, bis (di-n-propylamino) Dimethoxysilane, bis (methyl n-propylamino) dimethoxysilane, bis (ethyl n-propylamino) dimethoxysilane, diethylamino (di-n-propylamino) dimethoxysilane, diethylamino (diiso-propylamino) dimethoxysilane, bis (di iso-propylamino) dimethoxysilane, bis (methyliso-propylamino) dimethoxysilane, bis (ethyliso-propylamino) dimethoxysilane, bis (n-propylaminoiso-pro L-amino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, diethylamino (di-n-butylamino) dimethoxysilane, bis (diiso-butylamino) dimethoxysilane, diethylamino (diiso-butylamino) dimethoxysilane, bis (Di-tert-butylamino) dimethoxysilane, diethylamino (di-tert-butylamino) dimethoxysilane, bis (disec-butylamino) dimethoxysilane, diethylamino (disec-butylamino)
Dimethoxysilane, bis (di-n-pentylamino) dimethoxysilane, diethylamino (di-n-pentylamino) dimethoxysilane, bis (dicyclopentylamino) dimethoxysilane, diethylamino (dicyclopentylamino) dimethoxysilane, bis (di-n-hexylamino) ) Dimethoxysilane, diethylamino (di-n-hexylamino) dimethoxysilane, bis (dicyclohexylamino) dimethoxysilane, diethylamino (dicyclohexylamino) dimethoxysilane and the like. Among these, bis (diethylamino) dimethoxysilane is particularly preferred.

The organosilicon compound component [C] represented by the general formula (1) is easily synthesized by, for example, a di-equivalent reaction of tetramethoxysilane or dichlorodimethoxysilane with a magnesium salt or lithium salt of a hydrocarbon amine. be able to.

The organosilicon compound component [C] in the prepolymerization
Is usually used in a molar ratio of Si / Al to 0.01 to 2, preferably 0.1 to 2, with respect to the aluminum atom of the component [B].
1 to 1.

As the prepolymerization method, components [A],
The component [B] and the component [C] are mixed, and usually in the presence of a limited amount of ethylene or α-olefin, from 0 to 70%.
React at 0.1 ° C for 0.1 to 10 hours. The mixing order of each component is
Although not particularly limited, usually, component [A], component [B],
The order of component [C] is preferred.

After the prepolymerization, the solid may be washed with an inert hydrocarbon solvent such as n-heptane, filtered and separated, and used as a solid component of the catalyst for the main polymerization.

The effects of the prepolymerization include improvement of polymerization activity, improvement of stereoregularity of the polymer, and stabilization of the particle shape 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.
In some cases, even if a pretreated solid is prepared without using ethylene or α-olefin, the same effect as the prepolymerized solid may be obtained.

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.

This polymerization is carried out according to the following formula (D): General formula (2) or (3)
Is added to polymerize or copolymerize the α-olefin.

[0040]

Embedded image

[0041]

Embedded image (However, in (2) or (3), 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. )

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, and iso-pentyl. , Cyclopentyl group, n-hexyl group, cyclohexyl group 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 an ethyl group, an n-propyl group, an 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-
A propyl group such as a propyl group, a butyl group such as an iso-butyl group, a diethylamino 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. 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 (2), 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,

[0049]

Embedded image

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

As R ³ NH, as shown by the following chemical structural formula,

[0052]

Embedded image

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 includes perhydroquinoline, perhydroisoquinoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline and derivatives thereof. .

The organosilicon compound represented by the general formula (2) includes a perhydroquinolino compound represented by the general formula (4), a perhydrohydroquinolino compound represented by the general formula (5), (Per-hydroquinolino) represented by the formula (6) (per-hydroisoquinoli compound, 1,2,3,4-tetrahydroquinolino compound represented by the general formula (7),
1,2,3,4-tetrahydroisoquinolino compound represented by the general formula (8), and (1,2,3,4)
-Tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compound and the like.

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

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

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

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

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

The compound represented by the general formula (5) includes
Bis (perhydroisoquinolino) dimethoxysilane; and the like.

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

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

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

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

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

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

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

The compound represented by the general formula (7) 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.

Further, bis (perhydroindolino) dimethoxysilane, bis (perhydroindisoindolino)
Dimethoxysilane and the like.

Specific examples of the organosilicon compound represented by the general formula (2) 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 (3) include a perhydroquinolino compound represented by the general formula (10) and a perhydrohydroquinolino compound represented by the general formula (11). 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
Examples thereof include perhydroquinolinosilane compounds such as hydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, piperidino (perhydroquinolino) dimethoxysilane, and diethylamino (per-hydroquinolino) dimethoxysilane.

Ethyl (2-methylperhydroquinolino)
Dimethoxysilane, n-propyl (2-methylper-hydroquinolino) dimethoxysilane, iso-propyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Butyl (2-methylperhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane, iso-butyl (2-methylperhydroquinolino) dimethoxysilane, tert-butyl (2-methylperhydroquinolino) dimethoxysilane, sec-butyl (2-methylperhydroquinolino)
Dimethoxysilane, n-pentyl (2-methylper-hydroquinolino) dimethoxysilane, iso-pentyl (2
-Methylperhydroquinolino) dimethoxysilacyclopentyl (2-methylperhydroquinolino) dimethoxysilane, n-hexyl (2-methylperhydroquinolino)
Dimethoxysilane, cyclohexyl (2-methylperhydroquinolino) dimethoxysilane, texyl (2-methylperhydroquinolino) dimethoxysilane, n-octyl (2-methylperhydroquinolino) dimethoxysilane, n-decyl (2-methylperhydroquinolino) dimethoxysilane And 2-decalino (2-methylpa-hydroquinolino) dimethoxysilane, and 2-methylpa-hydroquinolinosilane compounds such as phenyl (2-methylpa-hydroquinolino) 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 perhydroquinolinosilane compounds such as propyl (8-methylperhydroquinolino) dimethoxysilane, iso-propyl (9-methylperhydroquinolino) dimethoxysilane, and iso-propyl (10-methylperhydroquinolino) dimethoxysilane.

Among the above compounds, ethyl (per-hydroquinolino) dimethoxysilane, n-propyl (per-hydroquinolino) dimethoxysilane, iso-propyl (per-hydroquinolino) dimethoxysilane, n-butyl (per-hydroquinolino) dimethoxysilane , Iso-butyl (perhydroquinolino) dimethoxysilane, ter
-Butyl (perhydroquinolino) dimethoxysilane, s
Compounds such as ec-butyl (per-hydroquinolino) dimethoxysilane, n-hexyl (per-hydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, and diethylamino (per-hydroquinolino) dimethoxysilalane 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 -Hydroxyisoquinolino) dimethoxysilane, phenyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolidimethoxysilane, diethylamino (perhydroisoquinolino) dimethoxysilane, etc. Norinosilane compound And the like.

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) Compounds such as dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane, diethylamino (per-hydroisoquinolino) dimethoxysilane are preferred.

Specific examples of the organosilicon compound represented by the general formula (3) include compounds represented by the following chemical structural formulas.

[0100]

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[0101]

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

The organosilicon compound component [D] represented by the general formula (2) is synthesized, for example, by reacting tetramethoxysilane or dichlorodimethoxysilane with two equivalents of a magnesium or lithium salt of an HNR secondary amine. can do. The component [D] represented by the general formula (3) can be synthesized by an equivalent reaction of an alkyltrimethoxysilane or an alkylchlorodimethoxysilane with a magnesium or lithium salt of an HNR secondary amine.

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

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

In the present invention, at the time of the main polymerization, it is preferable to carry out the polymerization by further adding the component [B] to the above preliminarily polymerized components. When the component [B] is used at the time of the 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 prepolymerized component.

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. ~
It is in the range of 3.0.

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

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

The catalyst of the present invention has high catalytic activity and high hydrogen sensitivity, and the obtained α-olefin polymer has high stereoregularity and wide molecular weight distribution. Regarding the molecular weight distribution, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn determined in terms of polystyrene by GPC measurement is 10 or more, more preferably 12 or more, and particularly preferably 15 or more.

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

[0112]

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

The α-olefin polymer obtained in the present invention has the same molecular weight distribution as the α-olefin polymer obtained with a conventional titanium trichloride type catalyst having a low polymerization activity and called the second generation catalyst. Therefore, the moldability is good, and there is no problem of 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. 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.

[0114]

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 determined according to ASTM.
230 ° C. measured according to D1238, 2.16
It represents the weight (g) of the molten polymer for 10 minutes under a load of Kg. H. I indicates the ratio (weight of insoluble polymer / weight of charged polymer × 100) when the polymer was subjected to an extraction test with boiling n-heptane for 6 hours. Melting point (Tm) is DSC
(SSC-5200 DSC-220 manufactured by Seiko Instruments Inc.
It measured using C). The measuring method was 10 ° C / min. From room temperature to 230 ° C. At a rate of 5 ° C., and kept as it is for 5 minutes, then from 230 ° C. to 40 ° C. at 5 ° C./min. After the temperature was lowered at a rate of 10 ° C / 40 ° C to 230 ° C,
min. And the melting point 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.
0, the temperature is 130 ° C. and o is based on TMS.
-Measured using dichlorobenzene solvent.

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

Synthesis Example of Organosilicon Compound Component [D] (Bis (perhydroisoquinolino) dimethoxysilane) A stirrer piece was placed in a 200 mL three-necked flask equipped with a dropping funnel. And the inside of the flask was sufficiently purged with nitrogen using a vacuum pump.
-Heptane 100 mL, decahydroisoquinoline 17.
9mL (0.12mol) is put in the dropping funnel.
75 mL of a 1.6 M butyl lithium hexane solution (0.1
2 mol). The butyllithium solution in the dropping funnel was slowly dropped into the flask while maintaining the temperature in the flask at 4 ° C. After completion of the dropping, continue at room temperature
The mixture was stirred for an hour to obtain a lithium salt of perhydroisoquinoline.

Next, a stirrer pipe was placed in a flask (capacity: 400 mL) equipped with a glass filter equipped with a dropping funnel.
After the flask was sufficiently purged with nitrogen using a vacuum pump, 60 mL of distilled and dehydrated n-heptane and 9 mL of tetramethoxysilane (0.06 mol
1), and the lithium salt of perhydroisoquinoline was placed in the dropping funnel. At room temperature, the lithium salt of perhydroisoquinoline in the dropping funnel was slowly dropped into the flask. After completion of the dropwise addition, stirring was continued at 40 ° C. for 2 hours, and further, stirring was performed at room temperature for 12 hours. After confirming that the target product was produced by gas chromatography, the precipitate was filtered. The solvent in the filtrate is sufficiently distilled off under reduced pressure, and then the product is purified by performing primary distillation and secondary distillation to obtain the desired product, bis (perhydroisoquinolino) dimethoxysilane. Obtained. This compound has a boiling point of 180 ° C./1 mmHg and a GC purity of 98.
5%.

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

(2) Pre-polymerization treatment In a 200-mL flask equipped with a stirrer, 100 mL of distilled and dehydrated n-heptane, 1.2 mmol of triethylaluminum as the organoaluminum compound component [B],
After sequentially injecting 0.2 mmol as bis (diethylamino) dimethoxysilane as the organosilicon compound component [C], 0.3957 mmol in terms of Ti atom was added to the n-heptane slurry of the catalyst solid component [A] obtained above. The mixture was added and aged at 23 ° C. for 10 minutes. Thereafter, propylene gas was fed into the flask at a flow rate of 100 mL / min at normal pressure, and a prepolymerization treatment was performed for 5 minutes. The PP / Cat ratio of the obtained prepolymerized solid was 1.15.

(3) Polymerization of Propylene In a 2 L stainless steel autoclave equipped with a stirrer, 0.005 mmol of n-heptane slurry of the prepolymerized catalyst solid component obtained above in terms of titanium atom was converted. And 2.1 mmol of triethylaluminum as the organoaluminum compound component [B] and 0.36 mmol of bis (perhydroisoquinolino) dimethoxysilane as the organosilicon compound component [D] component and then 0.12 MPa.
Of hydrogen and liquefied propylene (1.2 L) were introduced. The temperature of the autoclave was raised, and the polymerization was carried out for 1 hour while maintaining the internal temperature at 70 ° C.

After completion of the polymerization, unreacted propylene gas was released, and the polymer was dried under reduced pressure at 50 ° C. for 20 hours to obtain a white powdery polypropylene. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that bis (perhydroisoquinolino) dimethoxysilane was used instead of bis (diethylamino) dimethoxysilane as the component [C] in the prepolymerization treatment. Was. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated except that the component [C] was not used in the prepolymerization treatment. The results are shown in Table 1.

[0126]

【table 1】

[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] a solid catalyst component essentially containing magnesium, titanium, a halogen element and an electron donor, [B]
An organoaluminum compound component, and [C] a general formula (1)
An organosilicon compound component represented by the formula (Where R represents a hydrocarbon group having 1 to 8 carbon atoms). The α-olefin is prepolymerized with a catalyst comprising
A method for polymerizing α-olefins, comprising adding an organosilicon compound represented by the general formula (2) or (3) to polymerize or copolymerize α-olefins. Embedded image Embedded image (However, in (2) or (3), 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. )