JPH10251329A - Production of propylene block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer having high stereoregularity and wide mol.wt. distribution in high catalytic activity by copolymerizing propylene, etc., in the presence of a specific catalyst and subsequently copolymerizing propylene and one or more other α-olefins. SOLUTION: This method for producing a propylene block copolymer comprises copolymerizing propylene with one or more other α-olefins in the presence of a catalyst to produce the propylene polymer having an α-olefin content of <=10wt.%, and subsequently copolymerizing propylene with one or more other α-olefins to produce the propylene polymer having an α-olefin content of 10-40wt.%. The catalyst comprises (A) a catalyst solid component consisting essentially of magnesium, titanium, a halogen and an electron donor, (B) an organic aluminum compound component such as triethyl aluminum or trimethyl aluminum, and (C) an organic silicon compound component of formula I or formula II [R<1> is a 1-8C hydrocarbon; R<2> is a 2-24C hydrocarbon (amino), etc.; R<3> N is a >=7C polycyclic amino forming the skeleton together with N].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel catalyst comprising a single type of organosilicon compound having a specific structure as a catalyst component.
The present invention relates to a method for producing a propylene block copolymer having a wide molecular weight distribution.

[0002]

2. Description of the Related Art In order to use polypropylene as a structural material for automobiles and home electric appliances, it is required to have excellent rigidity and heat resistance, good mechanical properties, and excellent impact resistance. ing. For this reason, a propylene block copolymer produced by producing propylene by propylene polymerization in the former stage and then copolymerizing propylene with another α-olefin in the latter stage is used.

As a propylene block copolymer, polypropylene produced by pre-stage polymerization has a high stereoregularity, a high melting point, and the like. Further, in order to keep the surface uniformity of the molded product when molded, the molecular weight distribution of the polypropylene is reduced. It needs to be wide.

Heretofore, a highly active supported catalyst system comprising a catalyst solid component essentially containing magnesium, titanium, a halogen element, and an electron donor, an organometallic compound of a Group I-III group metal, and an electron donor. There have been proposed a number of methods for producing highly stereoregular polypropylene using the above method. Further, JP-A-62-11705, JP-A-63-259807
JP, JP-A-2-84404, JP-A-4-202505, JP-A-4-370103, and the like, particularly one or more branched alkyl groups or cycloalkyl groups as electron donors directly on silicon A polymerization catalyst characterized by using a bonded silicate compound is disclosed.

[0005] 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 improve this problem, Japanese Patent Application Laid-Open Nos. 63-245408 and 2-2322
07, JP-A-4-370103 and the like disclose 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. In the case of a polymerization reactor having a pressure resistance limit, the polymerization temperature must be lowered, and there is a problem that the production speed is adversely affected.

Further, Japanese Patent Application Laid-Open Nos. Hei 3-7703 and Hei 4-360
No. 06, JP-A-8-301920 discloses a polymerization method in which at least two kinds of organosilicon compounds giving different MFRs are mixed and used as a catalyst component, but either one of the catalyst components acts. And the effect of expanding the molecular weight distribution is not sufficient. Further, in this method, it is essential to use two or more types of catalyst components, so that the polymerization process, the polymerization apparatus, and the polymerization operation become more complicated.

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

Further, Japanese Patent Application Laid-Open Nos. 6-25336 and 7-90
No. 012, JP-A-7-97411 and the like disclose a method of using a nitrogen-containing heterocyclic-substituted organosilicon compound in which an arbitrary carbon atom in a heterocycle is directly bonded to a silicon atom. However, it does not describe the molecular weight distribution. JP-A-3-74393 and JP-A-7-173212 disclose a method using a monocyclic amino group-containing organosilicon compound, but do not disclose the molecular weight distribution. ,

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

[0010]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a method for producing a propylene block copolymer having a wide molecular weight distribution while maintaining high stereoregularity and a high melting point. The purpose is to provide.

[0011]

Technical Solution to Solve the Problems The present invention relates to [A] a catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] a general formula In the presence of a catalyst comprising the organosilicon compound component represented by (1) or (2),
(1) a step of polymerizing propylene or propylene with another α-olefin to produce a propylene polymer having an α-olefin content of 10% by weight or less, and (2) polymerizing propylene with another α-olefin. A propylene polymer having an α-olefin content of 10 to 40% by weight.

[0012]

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[0013]

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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 represents a polycyclic amino group having 7 or more carbon atoms which forms a skeleton together with a nitrogen atom. )

Further, the present invention provides a method for polymerizing propylene or propylene with another α-olefin in the presence of the above-mentioned catalyst, and subsequently, propylene and other α-olefin in the second step without deactivating the above-mentioned catalyst. The present invention relates to a method for producing a propylene block copolymer, which comprises conducting a gas phase copolymerization with an α-olefin.

In the present invention, a solid catalyst component essentially comprising magnesium, titanium, a halogen element, and an electron donor is used as the component [A]. The method for producing the solid catalyst component [A] is not particularly limited.
4590, JP-A-56-55405, JP-A-56-45909, JP-A-56-163102, JP-A-57-63310, JP-A-57-115408, JP-A-58-83006,
JP-A-58-83016, JP-A-58-138707, JP-A-59-149905, JP-A-60-23404, JP-A-60
-32805, JP-A-61-18330, JP-A-61-55104
And Japanese Patent Application Laid-Open Nos. 2-77413 and 2-117905.

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

As the component [A], catalyst solid components described in JP-A-60-152511, JP-A-61-31402, and JP-A-62-81405 achieve the effects of the present invention. It is particularly preferable in terms of performing. According to the production methods described above, an aluminum halide is reacted with a silicon compound, and a Grignard compound is further reacted to precipitate a solid. Aluminum halide that can be used in the above reaction is
Although anhydrous aluminum halide is preferable, it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water can also be used. Specific examples of aluminum halide include:
Examples thereof include aluminum trichloride, aluminum tribromide, and aluminum triiodide, and aluminum trichloride is particularly preferable.

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

The amount of the compound used in the reaction between the aluminum halide and the silicon compound is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3 in element ratio (Al / Si). It is preferred to use an active solvent. The reaction temperature is usually from 10 to 100 ° C, preferably from 20 to 80 ° C, and the reaction time is usually from 0.2 to 5 hours, preferably from 0.5 to 3 hours.

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

The amount of the magnesium compound used is usually from 0.5 to 3, preferably from 1.5 to 2.3, in terms of the element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound. Range. The reaction temperature is usually -50 to 100 ° C, preferably -20
~ 50 ° C, 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 further treated with a titanium halide compound, and (2) the solid is coexisted with a titanium halide compound and an electron donor. , And then a treatment with a titanium halide compound.

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

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

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

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

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

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

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

[0031]

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[0032]

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

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

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

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

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

R ³ N is a polycyclic amino group having 7 or more, preferably 7 to 40, more preferably 7 to 20 carbon atoms forming a skeleton together with a nitrogen atom. The polycyclic amino group may be a saturated polycyclic amino group or a polycyclic amino compound in which part or all of the ring is unsaturated. The nitrogen atom of the polycyclic amino group is directly bonded to the silicon atom of the organosilicon compound. That is, the hydrogen atom of the secondary amine R ³ NH is removed and Si and N are chemically bonded. In the general formula (1), the two R ³ N groups may be the same or different.

As specific examples of R ³ NH, as shown by the following chemical structural formulas, perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroacridine, perhydrophenidine Nantridine, perhydrobenzo
(g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline,
Perhydroaceisoquinoline, an amine compound such as perhydroiminostilbene, and a part of hydrogen atoms other than the nitrogen atom in the amine compound is an alkyl group
Examples thereof include amine compounds substituted with a phenyl group or a cycloalkyl group.

[0039]

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

[0041]

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

As the organosilicon compound represented by the general formula (1), a perhydroquinolino compound represented by the general formula (3), a perhydroisoquinolino compound represented by the general formula (4), (Perhydroquinolino) (perhydroisoquinolino) compound represented by (5), general formula (6)
1,2,3,4-tetrahydroquinolino compound represented by the general formula (7), 1,2,3,4-tetrahydroisoquinolino compound represented by the general formula (7), and represented by the general formula (8) ( 1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compound and the like.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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

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

Also, bis (2-methylperhydroquinolino) dimethoxysilane, bis (3-methylperhydroquinolino) dimethoxysilane, bis (4-methylperhydroquinolino) dimethoxysilane, bis (5-methylperhydroquinolino) Dimethoxysilane, bis (6-methylperhydroquinolino) dimethoxysilane, bis (7-methylperhydroquinolino) dimethoxysilane, bis (8-methylperhydroquinolino) dimethoxysilane, bis (9-methylperhydroquinolino) dimethoxysilane And bis (methyl-substituted perhydroquinolino) dimethoxysilane, such as bis (10-methylperhydroquinolino) dimethoxysilane.

Further, bis (2,3-dimethylperhydroquinolino) dimethoxysilane, bis (2,4-dimethylperhydroquinolino) dimethoxysilane, bis (2,5-dimethylperhydroquinolino) dimethoxysilane, bis (2 , 6-Dimethylperhydroquinolino) dimethoxysilane, bis (2,
7-dimethylperhydroquinolino) dimethoxysilane, bis (2,8-dimethylperhydroquinolino) dimethoxysilane, bis (2,9-dimethylperhydroquinolino) dimethoxysilane, bis (2,10-dimethylperhydroquinolino)
Dimethoxysilane, bis (3,4-dimethylperhydroquinolino) dimethoxysilane, bis (3,5-dimethylperhydroquinolino) dimethoxysilane, bis (3,6-dimethylperhydroquinolino) dimethoxysilanebis (3,7- Dimethyl perhydroquinolino) dimethoxysilane, bis (3,8-
Dimethylperhydroquinolino) dimethoxysilane, bis (3,9-dimethylperhydroquinolino) dimethoxysilane, bis (3,10-dimethylperhydroquinolino) dimethoxysilane, bis (4,5-dimethylperhydroquinolino)
Dimethoxysilane, bis (4,6-dimethylperhydroquinolino) dimethoxysilane, bis (4,7-dimethylperhydroquinolino) dimethoxysilane, bis (4,8-dimethylperhydroquinolino) dimethoxysilane, bis (4.9-dimethyl Perhydroquinolino) dimethoxysilane, bis (4,
10-dimethylperhydroquinolino) dimethoxysilane,
Bis (5,6-dimethylperhydroquinolino) dimethoxysilane, bis (5.7-dimethylperhydroquinolino) dimethoxysilane, bis (5,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (5,9-dimethylperhydroquinolino) dimethoxysilane, bis (5,10-dimethylperhydroquinolino) dimethoxysilane, bis (6,7-dimethylperhydroquinolino) dimethoxysilane, bis (6,8 -Dimethylperhydroquinolino) dimethoxysilane, bis (6,9-dimethylperhydroquinolino) dimethoxysilane, bis (6,10-dimethylperhydroquinolino) dimethoxysilane, bis (7,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (7,9-dimethylperhydroquinolino) dimethoxysilane, bis (7,10-dimethylperhydroquinolino) dimethoxysilane, bis (8,9-dimethylperhydroquinolino) dimethoxysilane, bis (8,10 -
Bis (dimethyl-substituted perhydroquinolino) dimethoxysilane such as dimethylperhydroquinolino) dimethoxysilane and bis (9,10-dimethylperhydroquinolino) dimethoxysilane.

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

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

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

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

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

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

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

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

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

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

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

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

Further, bis (2-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3-methyl-1,
2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6-methyl-1,2,3,4-tetrahydroquino Lino) dimethoxysilane, bis (7-methyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (8-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (9-methyl-1,2,3,4-tetrahydroquinolino)
And bis (methyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as dimethoxysilane.

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

Further, bis (2,3,4-trimethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (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-1,2,3,4-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
And bis (trimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as -1,2,3,4-tetrahydroquinolino) dimethoxysilane.

Further, bis (2,3,4,6-tetramethyl-1,2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,7-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,8-tetra Methyl-
1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,3,4,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,7-tetramethyl-1,2,3,4-tetrahydro Quinolino) dimethoxysilane, bis (3,4,6,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2 , 3,4-Tetrahydroquinolino) dimethoxysilane, bis (4,6,7,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6,7,9- Bis (tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane Methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane compound.

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

The compound represented by the general formula (7) includes
Bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (1-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3-methyl
-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (6-methyl-1,2,3 , 4-tetrahydroisoquinolino) dimethoxysilane, bis (7-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (8-methyl-1,2,3,4-tetrahydroisoquino) Lino) dimethoxysilane, bis (9-methyl-1,2,3,4-
Bis (methyl-substituted-1,2,3,4-tetrahydroisoquinolino) such as tetrahydroisoquinolino) dimethoxysilane
A dimethoxysilane compound is exemplified.

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

Further, bis (1,3,4-trimethyl-1,2,3,4-
Tetrahydroisoquinolino) dimethoxysilane, bis (1,3,6-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,7-trimethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (1,3,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,9-trimethyl-
1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,7- Trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4, 9-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,7-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4, 6,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,9-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis ( 6,7,8-trimethyl-1,2,3,4-tetrahydroisoquinolino dimethoxysilane, bis (6,7,9-trimethyl-1,2,3,4-tetrahydroisoquinolino Dimethoxysilane, bis (7,8,9-
And bis (trimethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane compounds such as trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4,6-tetramethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (1,3,4,7-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,4,8-tetramethyl-1,2,3,4- Tetrahydroisoquinolino) dimethoxysilane, bis (1,3,4,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,
6,7-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6,8-tetramethyl-
1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6 , 7,8-Tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,7,9-tetramethyl-1,2,3,4-
Bis (tetramethyl-substituted-1,2,3,4) such as tetrahydroisoquinolino) dimethoxysilane and bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane 4-tetrahydroisoquinolino) dimethoxysilane compound.

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

The compound represented by the general formula (8) includes
(1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (2-methyl-1,
2,3,4-tetrahydroquinolino) (1-methyl-1,2,3,4-
(Tetrahydroisoquinolino) dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (3-methyl-1,
2,3,4-tetrahydroisoquinolino) dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (4-
Methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (4-methyl-1,2,3,4-tetrahydroquinolino) (4-methyl-1,2,3,4-tetrahydroiso Quinolino)
Dimethoxysilane, (4-methyl-1,2,3,4-tetrahydroquinolino) (6-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (6-methyl-1,2, 3,4-tetrahydroquinolino) (6-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (6-methyl-1,2,3,4-
Tetrahydroquinolino) (7-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (7-methyl-1,
2,3,4-tetrahydroquinolino) (7-methyl-1,2,3,4-
(Tetrahydroisoquinolino) dimethoxysilane, (7-methyl-1,2,3,4-tetrahydroquinolino) (8-methyl-1,
2,3,4-tetrahydroisoquinolino) dimethoxysilane, (8-methyl-1,2,3,4-tetrahydroquinolino) (8-
Methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (8-methyl-1,2,3,4-tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroiso Quinolino)
Compounds such as dimethoxysilane and (9-methyl-1,2,3,4-tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane are exemplified.

Of the above compounds, (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane is preferred.

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

[0080]

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[0081]

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

[0083]

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[0084]

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

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

Ethyl (2-methylperhydroquinolino) dimethoxysilane, n-propyl (2-methylperhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane, n-butyl (2-methyl Perhydroquinolino) dimethoxysilane, iso-propyl (2-methylperhydroquinolino) dimethoxysilane,
ter-butyl (2-methylperhydroquinolino) dimethoxysilane, sec-butyl (2-methylperhydroquinolino) dimethoxysilane, n-pentyl (2-methylperhydroquinolino) dimethoxysilane, iso-pentyl (2-methylper Hydroquinolino) dimethoxysilane, cyclopentyl (2-methylperhydroquinolino) dimethoxysilane, n-
Hexyl (2-methylperhydroquinolino) dimethoxysilane, cyclohexyl (2-methylperhydroquinolino)
2-methyl perhydroquinolino silane compounds such as dimethoxy silane, texyl (2-methyl perhydroquinolino) dimethoxy silane, n-octyl (2-methyl perhydroquinolino) dimethoxy silane, phenyl (2-methyl perhydroquinolino) dimethoxy silane Is mentioned.

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

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

The compounds represented by the general formula (10) include ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) Dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, ter-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquino) Lino) dimethoxysilane, n-pentyl (perhydroisoquinolino) dimethoxysilane, iso-pentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroisoquinolino) dimethoxysilane, n-
Hexyl (perhydroisoquinolino) dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, texyl (perhydroisoquinolino) dimethoxysilane, n-octyl (perhydroisoquinolino)
Examples include perhydroisoquinolinosilane compounds such as dimethoxysilane, phenyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane, and diethylamino (per-hydroisoquinolino) dimethoxysilane.

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

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

Among the above compounds, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, n-butyl (Perhydroisoquinolino) dimethoxysilane, iso-
Butyl (perhydroisoquinolino) dimethoxysilane,
ter-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (per-hydroisoquinolino) dimethoxysilane And compounds such as diethylamino (perhydroisoquinolino) dimethoxysilalane.

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

[0095]

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[0096]

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The organosilicon compound component [C] represented by the general formula (1) is synthesized, for example, by reacting tetramethoxysilane or dichlorodimethoxysilane with two equivalents of a magnesium or lithium salt of a HNR secondary amine. can do. The component [C] represented by the general formula (2) can be synthesized by an equivalent reaction of an alkyltrimethoxysilane or an alkylchlorodimethoxysilane with a magnesium or lithium salt of an HNR secondary amine.

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

In the present invention, a crystalline polymer is produced by propylene homopolymerization or copolymerization of propylene with another α-olefin in the first step in the presence of the above-mentioned catalyst system. A propylene block copolymer can be produced by producing a rubbery copolymer by copolymerizing propylene and an α-olefin other than propylene in the second step without deactivating the catalyst system.

The first stage polymerization may be propylene homopolymerization or copolymerization of propylene with another α-olefin. As α-olefins, ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene-1, octene-1, styrene, 2 Acyclic monoolefins such as -methylstyrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, and 9-vinylanthracene. Also, cyclic monoolefins such as cyclopentene, cyclohexane, norbornene and the like can be mentioned. Examples include diolefins such as dicyclopentadiene, 5-ethylidene norbornene-2, 4-vinylcyclohexene, and 1,5-hexadiene.

The proportion of α-olefins other than propylene in the crystalline polymer obtained in the first stage polymerization is preferably such that the properties of polypropylene are not lost, for example, 10% by weight or less. When the proportion of α-olefins other than propylene in the crystalline polymer exceeds 10% by weight, low crystalline polymer by-products increase.

In the second stage polymerization, a rubbery copolymer is produced by copolymerizing propylene with an α-olefin other than propylene. As α-olefins, ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene-1, octene-1, styrene, 2 Acyclic monoolefins such as -methylstyrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, and 9-vinylanthracene. Also, cyclic monoolefins such as cyclopentene, cyclohexane, norbornene and the like can be mentioned. Examples include diolefins such as dicyclopentadiene, 5-ethylidene norbornene-2, 4-vinylcyclohexene, and 1,5-hexadiene.

The propylene obtained in the second step and other α-
The proportion of the rubbery copolymer with the olefin is usually 3 to 40% by weight, preferably 5 to 30% by weight based on the total amount of the block copolymer.
It is. The proportion of α-olefins other than propylene in the rubbery copolymer is preferably from 10 to 40% by weight.

The polymerization modes of the present invention include a slurry polymerization in an inert hydrocarbon solvent, a bulk polymerization in which a monomer in a liquid state is polymerized in a solvent, and a gas phase polymerization in which a monomer is brought into contact with a catalyst in a gaseous state. Alternatively, polymerization can be performed by combining these. Above all, it is preferable to perform the bulk polymerization in which the monomer in a liquid state is polymerized as a solvent in the first stage, and the gas phase polymerization in which the monomer is brought into contact with a catalyst in a gaseous state in the second stage.

In the bulk polymerization, it is preferable to carry out the polymerization under a temperature and pressure condition which can keep propylene or a mixed monomer of propylene and another α-olefin in a liquid state. The polymerization temperature is usually 30 to 90 ° C, preferably 50 to 80 ° C. The polymerization time is usually from 5 minutes to 5 hours.

The gas-phase polymerization is carried out under a temperature and pressure condition that can keep propylene or a mixed monomer of propylene and another α-olefin in a liquid state. Gas phase polymerization is usually
The pressure is from atmospheric pressure to 20 kg / cm ² , preferably from atmospheric pressure to 10 kg / cm ² . The polymerization temperature is usually 30 to 95 ° C, preferably 40 to 70 ° C.
° C. The polymerization time is usually 30 minutes to 10 hours, preferably 1 to 5 hours.

In the slurry polymerization, propylene or a mixed monomer of propylene and another α-olefin is introduced in the presence of an inert hydrocarbon. Inert hydrocarbons include propane, butane, pentane, hexane, heptane, octane and the like.

In order to control the molecular weight of the produced polymer, hydrogen may be added to the polymerization system as a chain transfer agent, if necessary. The amount of hydrogen used to produce the α-olefin polymer having the desired stereoregularity, melting point and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions, and is usually 0.05 to 3.0 hydrogen partial pressure. Range.

In the present invention, propylene or another α-olefin may be preliminarily polymerized according to the above-mentioned various polymerization methods, and then the main polymerization may be carried out. The effects of the pre-polymerization include an improvement in polymerization activity, an improvement in stereoregularity of the polymer,
Stabilization of the polymer particle shape can be mentioned. As a method of the prepolymerization, a pretreated solid can be prepared by previously contacting the catalyst solid component [A] with the organoaluminum compound component [B] and the organosilicon compound component [C] and washing the solid. Further, using the component [A] or the above pre-treated solid, the component [B] and the component [C]
A prepolymerized solid can be prepared by polymerizing a limited amount of ethylene or α-olefin in the presence of

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

The prepolymerization time is usually from 0.1 to 10 hours, and it is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the solid catalyst component. When the amount is less than 0.1 g per 1 g of the solid catalyst component, the main polymerization activity is not sufficient, the amount of catalyst residue increases, and the stereoregularity of the α-olefin polymer is not sufficient. If it exceeds 100 g, the polymerization activity and the crystallinity of the α-olefin polymer tend to decrease. The prepolymerization temperature is 0 to 100 ° C, preferably 10 to 90 ° C.
In the presence of each catalyst component. When the prepolymerization is performed at a high temperature exceeding 50 ° C., it is preferable to reduce the concentration of ethylene or α-olefin or to shorten the polymerization time. Otherwise, 0.1 to 1 g of solid catalyst component
It is difficult to control the production of 100 g of prepolymer,
In addition, polymerization activity is reduced by the main polymerization, and crystallinity of the obtained α-olefin polymer is reduced.

The amount of the organoaluminum compound component [B] used in the prepolymerization is usually 0.5 to 1000, preferably 1 to 100, in terms of Al / Ti molar ratio with respect to titanium atoms of the solid catalyst component.
It is. The amount of the organosilicon compound component [C] used is usually such that the molar ratio of Si / Al to the aluminum atom of component [B] is 0.01 to 1, preferably 0.08 to 0.5. At the time of prepolymerization, hydrogen can be allowed to coexist as necessary. In the present invention, when the above pre-treated solid or pre-polymerized solid is used as a solid catalyst component in the main polymerization, the component [C] can be omitted in the main polymerization.

The catalyst system has a high catalytic activity, and the obtained propylene block copolymer has a high stereoregularity and a high melting point and a wide molecular weight distribution. Regarding the molecular weight distribution, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn, as determined by GPC measurement in terms of polystyrene, is 15 or more, more preferably 20 or more, and particularly preferably 30 or more.

[0114]

The propylene block copolymer obtained by the present invention has high crystallinity and a wide molecular weight distribution, is excellent in mechanical properties such as rigidity, heat resistance and tensile strength of a molded product, and has a high shear strength when melted. Since the die swell value with respect to the speed is high, there is no problem of poor appearance of the molded article such as a flow mark. The propylene block polymer of the present invention is used not only alone, but also as a compounding material, blends with other plastics and elastomers, glass fiber, inorganic and organic fillers such as talc, and other crystal nucleating agents. It can be used in a mixture, and can exhibit excellent performance as a structural material for automobiles, home appliances, etc., although not particularly limited.

[Examples] Examples of the present invention will be described below. In the examples, the (co) polymerization reaction rate is the yield (g) of the produced polymer per 1 g of the catalyst solid and per hour.

The block ratio is the weight ratio of the copolymer in the whole polymer (copolymer yield / total polymer yield × 100%).
HI is the ratio of insolubles (Polymer weight / Polymer weight x 100%) when the polymer was subjected to Soxhlet extraction with boiling n-heptane for 6 hours. Melt fluidity (MI) is ASTM
230 ° C measured according to -D1238, under a load of 2.16 kg
Indicates the weight (g) of the molten polymer for 10 minutes.

The melting point (Tm) was measured using a DSC (manufactured by Seiko Instruments Inc.)
ASC-5200). As a measurement condition, in a propylene polymer, 10 mg was added at a rate of 10 ° C.
Temperature, and hold for 5 minutes.
The temperature was lowered at a rate of 5 ° C./min to 40 ° C., and the melting point was measured again when the temperature was raised to 40 to 230 ° C. at a rate of 10 ° C./min.

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

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

The measurement of the ethylene content in the resulting copolymer was carried out as follows. The sample was heated and melted on a hot plate of a hot press, cooled under pressure, and quenched in a water bath to form a film of about 30 μm. This film by infrared spectrophotometer to measure the peak of 974 cm ^-1 and 720 cm ^-1, on the basis of the previously prepared calibration curve, was calculated ethylene content.

The intrinsic viscosity [η] of the rubber component was measured as follows. A 20 mg sample is accurately weighed and placed in a 25 mL volumetric flask, followed by the addition of 20 mL of decalin containing 0.3% BHT. Dissolve the sample completely at 135 ° C, transfer 20 mL of this solution into a viscometer using a thermostat set at 135 ° C, and measure the transit time between the designated marked lines. The intrinsic viscosity [η] of the rubber component was measured using the viscosity equation.

Reference Example (Synthesis Method of Organosilicon Compound Component [C] Synthesis Example: Bisperhydroisoquinolinodimethoxysilane [BPHIQ
DMS]) The stirrer piece was placed in a 200 mL three-necked flask equipped with a dropping funnel, and the flask was sufficiently purged with nitrogen using a vacuum pump. Then, 100 mL of distilled and dehydrated n-heptane, decahydro Quinoline 17.9mL
(0.12 mol), and 75 mL (0.12 mol) of a 1.6 M butyllithium hexane solution was placed in the dropping funnel. While maintaining the temperature in the flask at 4 ° C., the butyllithium solution in the dropping funnel was slowly dropped into the flask. After completion of the dropwise addition, stirring was continued at room temperature for 12 hours to obtain a lithium salt of perhydroisoquinoline.

Next, a stirrer piece was placed in a flask with a glass filter (capacity: 400 mL) equipped with a dropping funnel, and the flask was sufficiently purged with nitrogen using a vacuum pump. -60 mL heptane,
8.9 mL (0.06 mol) of tetramethoxysilane was charged, and the above-mentioned lithium salt of perhydroisoquinoline was charged 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 was sufficiently distilled off under reduced pressure, and then the product was purified by primary and secondary distillation to obtain the desired product, bisperhydroisoquinolinodidimethoxysilane. The boiling point of this compound is 189.5 ° C / 3m
mHg, GC purity 96.5%.

Example 1 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride was added to 40 mL of toluene.
Next, 15 mmol of methyltriethoxysilane was added dropwise with stirring, and after the completion of the addition, the mixture was reacted at 25 ° C. for 1 hour. After cooling the reaction product to −5 ° C., 18 mL of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, keeping the temperature of the reaction solution within the range of −5 to 0 ° C. Was. 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 filtered off, toluene and
Washed with n-heptane. Next, 4.9 g of the obtained solid was suspended in 30 mL of toluene, and titanium tetrachloride 150 mm was added to this suspension.
ol and 3.3 mmol of di-n-heptyl phthalate were added and reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off and washed with toluene and then with n-heptane. Further, the solid was suspended again in 30 mL of toluene, 150 mmol of titanium tetrachloride was added, and the mixture was reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off, and the solid was washed with toluene and then with n-heptane. The titanium content in the obtained catalyst solid component is 3.55 wt%
Met. This solid was suspended in 80 mL of heptane to prepare a heptane slurry of a catalyst solid component.

(2) Prepolymerization In a 2 L stainless steel autoclave equipped with a stirrer, 2.7 mL (2.7 mmol) of a n-hexane solution of triethylaluminum [B] as a catalyst component was diluted with n-heptane in nitrogen. [C] After introducing 4.5 mL (0.45 mmol) of a bisperhydroisoquinolinodimethoxysilane solution of a catalyst component and 1 kg / cm ² of hydrogen at a gauge pressure, liquid propylene was added.
900 mL was charged. Next, the autoclave was transferred into a constant temperature water bath at 10 ° C., and stirring was started. After 10 minutes, 9.1 mg (A) of the solid component [A] catalyst solid component prepared in (1) above, which was previously charged in the capsule, was added. = 3.55wt%) and added at 10 ° C.
The pre-polymerization reaction was performed for minutes.

(3) Bulk polymerization of propylene alone (bulk polymerization) Immediately after completion of the prepolymerization, an autoclave was set in a thermostatic bath for main polymerization, set at 60 ° C for 6 minutes, and then at the same temperature for 50 minutes.
Bulk polymerization of propylene alone was performed. After the polymerization, when discharging the unreacted gas out of the system, after sufficiently replacing the inside with nitrogen, to maintain the pressure in the system to 0.2 kg / cm ² in gauge pressure, it was weighed yield of homopolymer, 149.4 g. 31.4 g of this was sampled for analysis.

(4) Ethylene-propylene copolymerization (gas phase polymerization) The temperature of the autoclave in which the inside of the system was maintained at a gauge pressure of 0.2 kg / cm ² was set to 40 ° C. At a ratio of 1: 2 (100 Ncc / min and 200 Ncc / min, respectively) into the autoclave, and the copolymerization pressure was adjusted to ² kg / cm ² by gauge pressure. The same temperature, when performing 4 hours copolymerization reaction at the same pressure, the polymerization pressure is to hold the 2 kg / cm ² in gauge pressure, and discharging the unreacted gas out of the system, at 40 ° C., 4 hours, copolymerization The reaction was performed. The obtained copolymer was dried at 60 ° C. for 20 hours under reduced pressure, and the weight was measured. As a result, the yield was 10.1 g.

(Preparation of rubber component) 5.0 g of ethylene-propylene block copolymer was precisely weighed, and
The copolymer was dissolved by transferring to a vessel containing 500 mL and heating. Next, the solution was allowed to stand at room temperature for 24 hours, and the solids released were separated by centrifugation.
The solution was transferred into mL and left at room temperature for 1 hour with stirring. After collecting the rubber-like precipitated solid with a glass filter, 60 ° C
For 20 hours under reduced pressure to obtain a rubber component. Table 1
Table 5 summarizes the polymerization conditions, the polymerization results, and the properties of the obtained copolymer.

Examples 2 to 4 The same procedure as in Example 1 was carried out except that the polymerization was carried out under the polymerization conditions shown in Table 1. Tables 2 to 5 summarize the polymerization results and the properties of the obtained copolymers.

Comparative Examples 1 to 3 The same procedure as in Example 1 was carried out except that the polymerization was carried out under the polymerization conditions shown in Table 1 using diisopropyldimethoxysilane (DIPDMS) as the component [C] as a catalyst. Tables 2 to 5 summarize the polymerization results and the properties of the obtained copolymers.

[0131]

[Table 1]

[0132]

[Table 2]

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

[Table 5]

Example 5 (1) The solid catalyst component [A] was prepared in the same manner as in Example 1. (2) Prepolymerization In a 2 L stainless steel autoclave equipped with a stirrer, 2.7 mL (2.7 mmol) of n-hexane solution of triethylaluminum [B] as a catalyst component and diluted with n-heptane in nitrogen [C] After 4.5 mL (0.45 mmol) of a bisperhydroisoquinolinodimethoxysilane solution of a catalyst component and 4.5 kg / cm ² of hydrogen at a gauge pressure were introduced, 900 mL of liquid propylene was charged. Next, the autoclave was transferred into a constant temperature water bath at 10 ° C., and stirring was started. After 10 minutes, 9.1 mg (A) of the solid component [A] catalyst solid component prepared in (1) above, which was previously charged in the capsule, was added. = 3.55wt%) at 10 ℃
A pre-polymerization reaction was performed for 10 minutes.

(3) Bulk polymerization of propylene alone (bulk polymerization) Immediately after the completion of the prepolymerization, an autoclave was set in a thermostatic bath for the main polymerization, and the temperature was set at 70 ° C. for 6 minutes, and then at the same temperature for 50 minutes.
Bulk polymerization of propylene alone was performed. After the polymerization, when discharging the unreacted gas out of the system, after sufficiently replacing the inside with nitrogen, to maintain the pressure in the system to 0.2 kg / cm ² in gauge pressure, were weighed yield of homopolymer, 181 g Met. In this
28 g were sampled for analysis.

(4) Ethylene-propylene copolymerization (gas phase polymerization) The temperature of the autoclave in which the system was maintained at a gauge pressure of 0.2 kg / cm ² was set at 70 ° C., and a mixed gas of ethylene and propylene was mixed at a volume ratio. At a ratio of 1: 3.3 (70 Ncc / min and 230 Ncc / min, respectively) into the autoclave, and the copolymerization pressure was adjusted to a gauge pressure of 2 kg / cm ² . The same temperature, carrying out the 1 hour copolymerization reaction at the same pressure, the polymerization pressure is to hold the 2 kg / cm ² in gauge pressure, and discharging the unreacted gas out of the system, at 70 ° C., 1 hour, copolymerization The reaction was performed. The obtained copolymer was dried at 60 ° C. for 1 hour under reduced pressure, and the weight was measured. The yield was 4.1 g.

(Preparation of Rubber Component) 5.0 g of an ethylene-propylene block copolymer was precisely weighed, and
The copolymer was dissolved by transferring to a vessel containing 500 mL and heating. Next, the solution was allowed to stand at room temperature for 24 hours, and the solids released were separated by centrifugation.
The solution was transferred into mL and left at room temperature for 1 hour with stirring. After collecting the rubber-like precipitated solid with a glass filter, 60 ° C
For 20 hours under reduced pressure to obtain a rubber component. Table 6-
Table 13 summarizes the polymerization conditions, the polymerization results, and the properties of the obtained copolymer.

Examples 6 to 16 The same procedures as in Example 5 were carried out except that the polymerization was carried out under the polymerization conditions shown in Table 6. Tables 7 to 9 summarize the polymerization results and the properties of the obtained copolymers.

Examples 17 to 28 The same procedures as in Example 5 were carried out except that the polymerization was carried out under the polymerization conditions shown in Table 10. Tables 10 to 13 summarize the polymerization results and the properties of the obtained copolymers.

Comparative Examples 4 to 7 Comparative examples 4 to 7 were carried out in the same manner as in Example 5, except that cyclohexylmethyldimethoxysilane (CMDMS) was used as the component [C] under the polymerization conditions shown in Table 14. Table 1
Tables 5 to 17 summarize the polymerization results and the properties of the obtained copolymers.

[0143]

[Table 6]

[0144]

[Table 7]

[0145]

[Table 8]

[0146]

[Table 9]

[0147]

[Table 10]

[0148]

[Table 11]

[0149]

[Table 12]

[0150]

[Table 13]

[0151]

[Table 14]

[0152]

[Table 15]

[0153]

[Table 16]

[0154]

[Table 17]

[Brief description of the drawings]

FIG. 1 is a chart showing a preparation method and a polymerization method of a catalyst of the present invention.

Claims (2)

[Claims] 1. [A] a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor, [B]
Organoaluminum compound component, and [C] general formula
(1) Propylene or propylene and another α-olefin are polymerized in the presence of a catalyst comprising the organosilicon compound component represented by (1) or (2), and the α-olefin content is 10% by weight or less. And (2) polymerizing propylene with another α-olefin to produce a propylene polymer having an α-olefin content of 10 to 40% by weight. For producing a propylene block copolymer. Embedded image Embedded image (However, in (1) or (2), R ¹ has 1 to ¹ carbon atoms.
8 represents a hydrocarbon group, and R ² represents a hydrocarbon group having ² to 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or 1 carbon atom.
Shows the 24 hydrocarbon alkoxy group, R ³ N represents a polycyclic amino group having 7 or more carbon atoms in a backbone together with a nitrogen atom. ) 2. Polymerization of propylene or propylene with another α-olefin in the presence of the catalyst according to claim 1, followed by propylene and propylene in a second stage without deactivating said catalyst. A method for producing a propylene block copolymer, comprising performing gas phase copolymerization with another α-olefin.