JP2000186110A - Production of ethylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer having a wide molecular weight distribution in a wide molecular weight range by copolymerizing ethylene with an α-olefin in the presence of a catalyst composed of a catalytic solid component, an organoaluminum compound component and a specific organosilicon compound component. SOLUTION: Ethylene is copolymerized with an α-olefin in the presence of a catalyst comprising (A) a catalytic solid component essentially composed of magnesium, titanium and a halogen element, (B) an organoaluminum compound component and (C) an organosilicon compound component of formula I or formula II (R1 is a 1-8C hydrocarbon; R2 is a 2-24C hydrocarbon or the like; R3N is a 7-40C polycyclic amino forming a skeleton with nitrogen) to give the objective copolymer having 11-95 wt.% ethylene content. The component A is obtained by reacting an aluminum halide with a silicon compound preferably at 20-80 deg.C for 0.5-3 hours, reacting a Grignard compound and precipitating a solid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an ethylene copolymer having a wide molecular weight distribution and a wide molecular weight distribution in various polymerization processes using a highly active polymerization catalyst.

[0002]

2. Description of the Related Art In recent years, in order to (co) polymerize ethylene, magnesium, titanium, a halogen element, and, if necessary, a solid catalyst component which essentially requires an electron donor, and an organic material of a group 1 to 3 metal in the periodic table. Many supported high-activity catalyst systems comprising a metal compound and, if necessary, an electron donor as a third component have been proposed. However, the ethylene (co) polymer obtained by using the above-mentioned supported catalyst system usually has a narrow molecular weight distribution, a low polymer melt tension, poor flowability in blow molding and extrusion molding, and furthermore, a molded product having a low flowability. Mechanical properties, appearance, etc. become problems.

In order to improve this problem, it is desirable to increase the molecular weight distribution of the ethylene (co) polymer,
Various means have been proposed. Numerous proposals include JP-A-57-128707, JP-A-60-177008, JP-A-63-75009, JP-A-7-138321, and JP-A-7-138321.
-126316, 7-258326, 7-25
No. 8327, No. 8-245716, No. 8-22561
In each of the publications 2, polymerization using a plurality of polymerization vessels or
A method of expanding the molecular weight distribution by multistage polymerization has been adopted. 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 an ethylene (co) polymer having a low molecular weight and a wide molecular weight distribution in a plurality of reactors, an excess amount of a chain transfer agent such as hydrogen is used in one reactor to produce a low molecular weight polymer. And there is a problem that affects the production speed.

Japanese Patent Application Laid-Open No. 8-188613 proposes a method for producing an ethylene (co) polymer having a wide molecular weight distribution by using a specific and improved solid catalyst component. However, none of the solid catalysts has a sufficient effect of expanding the molecular weight distribution.

[0005] In the α-olefin polymer,
JP-A-8-120021 and JP-A-8-143621 disclose a method in which a cyclic aminosilane compound is used as a catalyst component together with an organoaluminum compound.
Nos. 703 and 4-136006 are different M
Polymerization methods using at least two types of electron donors that provide FR as a catalyst component are disclosed, but the effect of expanding the molecular weight distribution is not sufficient for these methods,
Further, regarding the ethylene (co) polymer, the effect of expanding the molecular weight distribution is unknown.

Further, as a method for producing an ethylene (co) polymer having a wide molecular weight distribution, a conventional low molecular weight ethylene (co) polymer having a narrow molecular weight distribution and a high molecular weight ethylene (co) polymer are prepared in advance. Then, a method of melting and mixing them is conceivable, but also in this case, relatively high fluidity,
That is, in order to produce an ethylene (co) polymer having a relatively low molecular weight and a wide molecular weight distribution, it is necessary to uniformly melt-mix the low molecular weight ethylene (co) polymer and the very high molecular weight ethylene (co) polymer. Is very difficult, and the generation of fish eyes and gels becomes a problem.

[0007]

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide an ethylene copolymer having a wide molecular weight distribution in a wide molecular weight range.

[0008]

[Technical Means for Solving the Problems] The present invention relates to [A] a catalyst solid component essentially containing magnesium, titanium and a halogen element, [B] an organoaluminum compound component, and [C] a general formula (1) or In the presence of a catalyst comprising the organosilicon compound component represented by (2), ethylene and an α-olefin are copolymerized to have an ethylene content of 11 to 95.
The present invention relates to a method for producing an ethylene copolymer, which comprises producing an ethylene copolymer in an amount of 0.1% by weight. (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 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or 1 carbon atom. ~ 24
R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.)

Further, in the present invention, [A] magnesium,
Titanium, a halogen element, and general formula (1) or (2)
In the presence of a catalyst solid component essentially comprising an organosilicon compound represented by the formula: and [B] an organoaluminum compound component, ethylene and an α-olefin are copolymerized to have an ethylene content of 11 to 95% by weight. % Of an ethylene copolymer, and a method for producing the ethylene copolymer. (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 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or Represents a hydrocarbon alkoxy group having 1 to 24 carbon atoms, and R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.)

[0010]

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[0011]

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In the present invention, a solid catalyst component essentially containing magnesium, titanium and a halogen element is used as the component [A]. The method for producing the solid catalyst component [A] is not particularly limited, and examples thereof include JP-A-54-94590 and JP-A-54-94590.
6-55405, 56-45909, 56-1
63102, 57-63310, 57-115
No. 408, No. 58-83006, No. 58-83016
No. 58-138707, No. 59-149905
No. 60-23404, No. 60-32805, No. 61-18330, No. 61-55104,
-77413, 2-117905, and the like. Typical production methods include (1) magnesium compounds such as magnesium chloride,
A method of co-milling 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 a titanium halide compound is added to the solution to precipitate a catalyst solid. And the like.

The component [A] includes Japanese Patent Publication No. 58-172.
No. 06, No. 59-49242, JP-A-60-1525
The catalyst solid components described in JP-A-11-61, JP-A-61-31402, and JP-A-62-81405 are preferable for achieving the effects of the present invention. According to the production methods described above, first, an aluminum halide is reacted with a silicon compound, and then a Grignard compound is reacted to precipitate a solid. 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 dimethyltrimethylsilane. 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 determined by the element ratio (Al / Si)
And usually 0.4 to 1.5, preferably 0.7 to 1.
In the reaction, it is preferable to use an inert solvent such as hexane or toluene. The reaction temperature is generally 10 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is generally 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, as the 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 the titanium halide compound and the electron donor. , And then a treatment with a titanium halide compound.

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

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

The electron donor used in the contact treatment is a Lewis basic compound, preferably an aromatic diester, particularly preferably an orthophthalic diester. Specific examples of the orthophthalic diester include diethyl orthophthalate, di-n-butyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, di-n-hexyl orthophthalate, di-2-ethylhexyl orthophthalate, di-n-heptyl orthophthalate, and orthophthalate. And di-n-octyl acid.

After the above-mentioned contact treatment, the treated solid is generally separated from the treated mixture, and the solid obtained by sufficiently washing with an inert solvent is used as the catalyst solid component [A] of the present invention as an ethylene copolymerization catalyst. Can be used. The shape of the component [A] is particularly important when ethylene is copolymerized in the gas phase, and it is desirable that the shape is spherical with a relatively narrow particle size distribution. Therefore, the component [A] can be prepared by controlling the reaction or the treatment temperature and speed at the stage of formation and precipitation of the solid. Further, in order to easily control the solid form, the component [A] can be prepared using a metal oxide as a carrier. The metal oxide is preferably porous, and examples thereof include clays such as silica, alumina, silica-alumina, magnesia, and zeolite, minerals, and zirconia. For metal oxide carriers,
The method for supporting a solid component containing magnesium, titanium, a halogen element, or the dimethoxysilane compound of the present invention is not particularly limited. For example, JP
-48584, 59-142208, 61-55
No. 105, No. 61-87703, No. 62-190204
No. 55-112891, No. 58-120617,
Nos. 57-44611, 64-54008, 62-
No. 256802, No. 54-62292, No. 59-870
No. 7, No. 60-133011, JP-A-3-72956
No., No. 4-261410, No. 2-302408, No. 3
The method proposed in each publication of -33103 can be adopted.

As the organoaluminum compound as the component [B] of the present invention, alkylaluminum, alkylaluminum halide and the like can be used. Alkylaluminum is preferable, and trialkylaluminum is particularly preferable. Examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. 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 used as the ethylene copolymerization catalyst is 0.1 to 1000, preferably 10 to 400, in terms of the element ratio (Al / Ti) of titanium in the solid catalyst component [A] to titanium.

The component [C] of the present invention is an organosilicon compound represented by the general formula (1) or (2). (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 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or 1 carbon atom. ~ 24
R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom.)

[0026]

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[0027]

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R ^{1 in the} organosilicon compound component represented by the general formula (1) or (2) is a hydrocarbon group having 1 to 8 carbon atoms, and is an unsaturated or saturated aliphatic hydrocarbon having 1 to 8 carbon atoms. And the like.

Specific examples include a methyl group, an ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, i
Examples thereof include a so-butyl group, a ter-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group. Particularly preferred is a methyl group.

In the general formula (2), R ² has ^{2 to 2} carbon atoms.
4 preferably 2 to 8 hydrocarbon groups, 2 to 24 carbon atoms, preferably 2 to 8 hydrocarbon amino groups, or 1 to 2 carbon atoms
4 preferably 1 to 8 hydrocarbon alkoxy groups. Among them, a hydrocarbon group having 2 to 24 carbon atoms or 2 to 24 carbon atoms
A hydrocarbon amino group.

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

Specific examples of the hydrocarbon amino group having 2 to 24 carbon atoms include a dimethylamino group, a methylethylamino group,
Diethylamino group, ethyl n-propylamino group, di-n
-Propylamino group, ethylisopropylamino group, diisopropylamino group, pyrrolidino group, piperidino group,
Hexamethyleneimino group and the like.

Specific examples of the hydrocarbon alkoxy group having 1 to 24 carbon atoms include methoxy, iso-propoxy, t
er-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 (1), the two R ³ N groups may be the same or different.

As a specific example of R ³ NH, as shown by the following chemical structural formula,

[0038]

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Perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroacridine,
Perhydrophenanthridine, perhydrobenzo (g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline,
Perhydrobenzo (h) isoquinoline, perhydrobenzo
(f) isoquinoline, perhydroacequinoline, perhydroaceisoquinoline, an amine compound such as perhydroiminostilbene, and further, in the amine compound, a part of hydrogen atoms other than a nitrogen atom is an alkyl group, a phenyl group, Examples thereof include amine compounds substituted with a cycloalkyl group.

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

[0041]

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

Particularly preferred R ³ NH 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), (Per-hydroquinolino) represented by the formula (5) (per-hydroisoquinoli compound, 1,2,3,4-tetrahydroquinolino compound represented by the general formula (6),
1,2,3,4-tetrahydroisoquinolino compound represented by the general formula (7), and (1,2,3,4
-Tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compound and the like.

[0045]

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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,
Examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a ter-butyl group and a sec-butyl group. The hydrocarbon substituent on the saturated ring of R ³ N may be one or more.

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

Further, bis (2-methylperhydroquinolino) dimethoxysilane, bis (3-methylperhydroquinolino) dimethoxysilane, bis (4-methylperhydroquinolino) dimethoxysilane, bis (5-methylperhydroquinolino) dimethoxysilane,
(Hydroquinolino) dimethoxysilane, bis (6-methylperhydroquinolino) dimethoxysilane, bis (7-methylperhydroquinolino) dimethoxysilane, bis (8
-Methylper-hydroquinolino) dimethoxysilane, bis (9-methylper-hydroquinolino) dimethoxysilane,
Examples include bis (methyl-substituted per-hydroquinolino) dimethoxysilane such as bis (10-methylper-hydroquinolino) dimethoxysilane.

Further, bis (2,3-dimethylperhydroquinolino) dimethoxysilane, bis (2,4-dimethylperhydroquinolino) dimethoxysilane, bis (2,5
-Dimethylperhydroquinolino) dimethoxysilane, bis (2,6-dimethylperhydroquinolino) dimethoxysilane, bis (2,7-dimethylperhydroquinolino)
Dimethoxysilane, bis (2,8-dimethylperhydroquinolino) dimethoxysilane, bis (2,9-dimethylperhydroquinolino) dimethoxysilane, bis (2,1
0-dimethylperhydronorino) dimethoxysilane, bis (3,4-dimethylperhydroquinolino) dimethoxysilane, bis (3,5-dimethylperhydroquinolino)
Dimethoxysilane, bis (3,6-dimethylperhydroquinolino) dimethoxysilanebis (3,7-dimethylperhydroquinolino) dimethoxysilane, bis (3,8-
Dimethyl per-hydroquinolino) dimethoxysilane, bis (3,9-dimethyl per-hydroquinolino) dimethoxysilane, bis (3,10-dimethyl per-hydroquinolino)
Dimethoxysilane, bis (4,5-dimethylperhydroquinolino) dimethoxysilane, bis (4,6-dimethylperhydroquinolino) dimethoxysilane, bis (4,7
-Dimethylperhydroquinolino) dimethoxysilane, bis (4,8-dimethylperhydroquinolino) dimethoxysilane, bis (4.9-dimethylperhydroquinolino)
Dimethoxysilane, bis (4,10-dimethylperhydroquinolino) dimethoxysilane, bis (5,6-dimethylperhydroquinolino) dimethoxysilane, bis (5.
7-dimethylper-hydroquinolino) dimethoxysilane,
Bis (5,8-dimethylper-hydroquinolino) dimethoxysilane, bis (5,9-dimethylper-hydroquinolino) dimethoxysilane, bis (5,10-dimethylpar-
(Hydroquinolino) dimethoxysilane, bis (6,7-dimethylperhydroquinolino) dimethoxysilane, bis (6,8-dimethylperhydroquinolino) dimethoxysilane, bis (6,9-dimethylperhydroquinolino) dimethoxysilane, bis (6,10- Dimethylper-hydroquinolino) dimethoxysilane, bis (7,8-dimethylper-hydroquinolino) dimethoxysilane, bis (7,9
-Dimethylper-hydroquinolino) dimethoxysilane, bis (7,10-dimethylper-hydroquinolino) dimethoxysilane, bis (8,9-dimethylper-hydroquinolino) dimethoxysilane, bis (8,10-dimethylpar-
Hydroquinolino) dimethoxysilane, bis (9,10-
Bis (dimethyl-substituted per-hydroquinolino) dimethoxysilane such as dimethylper-hydroquinolino) dimethoxysilane.

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

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

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

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

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

Further, bis (1,3-dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,4-dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,5-dimethylper-hydroisoquinolino) Dimethoxysilane, bis (1,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,7-dimethylpar-
(Hydroisoquinolino) dimethoxysilane, bis (1,8
-Dimethylper-hydroisoquinolino) dimethoxysilane, bis (1,9-dimethylper-hydroisoquinolino)
Dimethoxysilane, bis (1,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,5-dimethylperhydroisoquinolino) dimethoxysilane , Bis (3,6-dimethylper-hydroisoquinolino) dimethoxysilane, bis (3,7-dimethylper-hydroisoquinolino) dimethoxysilane, bis (3
8-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,9-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (3,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,5-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,6-dimethylpa-hydroisoquinolino) dimethoxysilane , Bis (4,7-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4
9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (4,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,6-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,7-
Dimethyl per-hydroisoquinolino) dimethoxysilane,
Bis (5,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (5,10-dimethylper-hydroisoquinolino) dimethoxysilane, bis ( 6,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,9-dimethylpar-
Hydroisoquinolino) dimethoxysilane, bis (6.1
0-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,8-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,9-dimethylper-hydroisoquinolino) dimethoxysilane, bis (7,10
-Dimethylper-hydroisoquinolino) dimethoxysilane, bis (8,9-dimethylper-hydroisoquinolino)
Dimethoxysilane, bis (8,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (9,10-
Bis (dimethyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as dimethylper-hydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4-trimethylpar-
Hydroisoquinolino) dimethoxysilane, bis (3,
4,5-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (4,5,6-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (5,6,7-trimethylpa-hydroisoquinolino) Dimethoxysilane,
Bis (6,7,8-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (7,8,9-trimethylpa-hydroisoquinolino) dimethoxysilane, bis (8,9,10-trimethylpa-hydro) Isoquinolino)
Examples include bis (trimethyl-substituted per-hydroisoquinolino) dimethoxysilane compounds such as dimethoxysilane.

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

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

As the compound represented by the general formula (5),
(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 (6) includes
Bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like can be mentioned.

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

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

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

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

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

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

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

[0069]

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[0070]

Embedded image Examples of the organosilicon compound represented by the general formula (2) include a per-hydroquinolino compound represented by the general formula (9) and a per-hydroisoquinolino compound represented by the general formula (10).

[0071]

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R^FourIs R^ThreeRepresents a substituent on a saturated ring of N,
Elemental or unsaturated or saturated aliphatic having 1 to 24 carbon atoms
It is a hydrocarbon group. R^FourAre preferably hydrogen,
Tyl group, ethyl group, n-propyl group, iso-propyl
Group, n-butyl group, iso-butyl group, ter-butyl group
Group, sec-butyl group and the like. Also, R ^ThreeN
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 (particulate
(Hydroquinolino) dimethoxysilane, cyclohexyl (perhydroquinolino) dimethoxysilane, texyl (perhydroquinolino) dimethoxysilane, n-octyl (perhydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, piperidino (pa-hydroquinolino) dimethoxy Perhydroquinolinosilane compounds such as silane and diethylamino (perhydroquinolino) dimethoxysilane are exemplified.

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

Iso-propyl (3-methylperhydroquinolino) dimethoxysilane, iso-propyl (4-
Methyl per-hydroquinolino) dimethoxysilane, iso
-Propyl (5-methylperhydroquinolino) dimethoxysilane, iso-propyl (6-methylperhydroquinolino) dimethoxysilane, iso-propyl (7-methylperhydroquinolino) dimethoxysilane, iso-
Examples include methyl-substituted 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 (2) include compounds represented by the following chemical structural formulas.

[0082]

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[0083]

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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 in a mixture of isomers as the component [C] of the present invention.

The organosilicon compound component [C] represented by the general formula (1) can be prepared, for example, by reacting tetramethoxysilane or dichlorodimethoxysilane with two equivalents of a magnesium or lithium salt of a secondary amine of HNR ³ . Can be synthesized. The component [C] represented by the general formula (2) can be synthesized by an equivalent reaction between alkyltrimethoxysilane or alkylchlorodimethoxysilane and a magnesium or lithium salt of HNR ³ secondary amine.

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

In the present invention, ethylene can be copolymerized using the components [A], [B] and [C]. The solid catalyst component [A] may contain the same component as the component [C] in addition to magnesium, titanium and halogen, and copolymerization of ethylene only with the component [A] and the component [B]. Can be performed. The solid catalyst component [A] containing the component [C] may be used as, for example, the component [C] as an electron donor in the above-described method for preparing the solid catalyst component [A].
Can be prepared. Also,
As a method for preparing the solid catalyst component [A] containing the component [C], as described later, the component [A] is contact-treated with the component [B] and the component [C] in advance, and the pretreated solid is washed. There is a method.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used to produce an ethylene copolymer having a desired melting point and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions, but is usually 0.001 MPa to 3 MPa, preferably a hydrogen partial pressure of preferably 0.001 MPa to 3 MPa. It is in the range of 0.01 to 1 MPa. During ethylene polymerization, there is no particular limitation on the order of contact of each catalyst component,
Component [A] and component [B] or component [B] and component [C]
Are preferably brought into contact beforehand with the component [A] or the component [C].

In the present invention, ethylene copolymer means the melting point of the polymer when producing a crystalline ethylene copolymer.
To lower the density, transparency of the film, copolymerization with α-olefins for the purpose of increasing the impact resistance, and copolymerization with α-olefins to produce an amorphous entropy elastic body, Furthermore, terpolymerization with an α-olefin and a non-conjugated diene for introducing an unsaturated bond into the polymer is included. As the α-olefin, propylene, 1
-Butene, 1-hexene, 4-methylpentene-1,1
-Octene and non-conjugated dienes include cyclopentadiene, cyclohexadiene, hexadiene, heptadiene, ethylidene norbornene, dicyclopentadiene and the like.

As the polymerization method in the present invention, propane,
A slurry polymerization method or a high-temperature solution method using a nonpolar solvent such as butane, pentane, hexane, heptane or octane, a gas phase polymerization method in which monomers are polymerized by contacting a monomer in a gaseous state with a catalyst, or a liquefied monomer is dissolved in a solvent. For example, a bulk polymerization method in which polymerization is performed therein, a high-temperature high-pressure tubular method, an autoclave method, or the like can be used.

In the above polymerization method, either continuous polymerization or batch polymerization may be performed. The polymerization pressure is 0.1 to 10
MPa, preferably 1 to 6 MPa, and 5 in the high pressure method.
-300 MPa, preferably 10-200 MPa.

The polymerization temperature is from 10 to 120 ° C., preferably from 30 to 100 ° C., more preferably from 60 to 90 ° C .;
The temperature is 250 ° C, more preferably 130 to 220 ° C.
The polymerization time is generally 0.1 to 10 hours, preferably 0.5 to 10 hours.
The temperature ranges from 1 to 1200 seconds, preferably from 20 to 600 seconds for high-temperature and high-pressure polymerization.

In the present invention, it is preferable to conduct ethylene copolymerization after preliminarily (co) polymerizing ethylene alone or ethylene and α-olefin according to the above-mentioned various polymerization methods. The effects of the prepolymerization include improvement of polymerization activity and stabilization of the particle shape of the polymer. As a method of the prepolymerization, the catalyst solid component [A] is previously contact-treated with the organoaluminum compound component [B] and the organosilicon compound component [C], and the pretreated solid can be prepared by washing the solid. Further, the catalyst solid component [A]
Alternatively, a prepolymerized solid can be prepared by polymerizing a limited amount of monomer in the presence of the organoaluminum compound component [B] and the organosilicon compound component [C] using the pretreated solid. .

In the present invention, when the above-mentioned pretreated solid or prepolymerized solid is used as the catalyst solid component [A] in the copolymerization, the organosilicon compound component [C] can be omitted in the copolymerization.

In the preliminary contact treatment of the present invention, the components [A], [B] and [C] are mixed,
React at １００100 ° C. for 0.1 to 10 hours. The mixing order of each component is not particularly limited, but usually, the order of component [A], component [B], and component [C] is preferable. After the contact treatment, the solid is washed with an inert hydrocarbon solvent such as n-heptane, filtered and separated, and used as a catalyst solid component for prepolymerization or copolymerization.

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 separated and then used for copolymerization, or the copolymerization can be carried out without separation.

The prepolymerization time is usually 0.1 to 10 hours, and it is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the solid catalyst component. If the amount is less than 0.1 g per 1 g of the solid catalyst component, the copolymerization activity is not sufficient, the amount of the catalyst residue increases, and the control of the particle shape is not sufficient. On the other hand, if it exceeds 100 g, the equipment for supplying the solid catalyst component to the polymerization reactor becomes large, and it is difficult to control the supply. The pre-polymerization temperature is from 0 to 100
C., preferably 10-90.degree. C., in the presence of each catalyst component. When pre-polymerization 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, it is difficult to control the production of 0.1 to 100 g of the prepolymer per 1 g of the solid catalyst component, and the polymerization activity is reduced by copolymerization.

The amount of the organoaluminum component used in the prepolymerization is usually Al / Al with respect to the titanium atom of the catalyst solid component.
Ti molar ratio is 0.5 to 1000, preferably 1 to 100
It is. The amount of the organosilicon compound used is usually Si / A with respect to the aluminum atom of the organoaluminum compound component.
The molar ratio is from 0.01 to 1, preferably from 0.08 to 0.5
It is. At the time of prepolymerization, hydrogen can be allowed to coexist as necessary.

The present catalyst system has a high catalytic activity, and the obtained ethylene copolymer has a wide molecular weight distribution. The molecular weight distribution is such that the ratio Mw / Mn of the weight-average molecular weight Mw and the number-average molecular weight Mn, determined in terms of polystyrene by GPC measurement, is 7 or more, more preferably 10 or more, and particularly preferably 1 or more.
4 or more.

The ethylene copolymer produced by the ethylene copolymerization according to the present invention has an ethylene content of 11 to 95% by weight, preferably 20 to 90% by weight, particularly preferably 30 to 70% by weight. is there.

The ethylene copolymer of the present invention has a good melt fluidity and a large melt viscoelasticity, so that injection molding, vacuum molding and blow molding are easy, the mechanical properties of the molded body are excellent, and there are few problems in appearance. . In addition to using the ethylene copolymer of the present invention alone, many other plastics,
Blends with elastomers, as well as reinforcing agents for inorganic and organic fillers such as glass fiber, and other nucleating agents can be mixed and used.

[0102]

According to the present invention, when ethylene is copolymerized using the catalyst of the present invention, ethylene having a high polymerization activity, a wide molecular weight, that is, a wide molecular weight distribution in a wide range of MFR values, and a high viscoelasticity at the time of melting. A copolymer can be produced.

[0103]

EXAMPLES In the examples, "polymerization activity" refers to the yield (g) of the produced polymer per 1 g of Ti in the catalyst solid. MFR is defined as 2.1 according to ASTM D-1238.
It is a melting index (g / 10 min.) Of a polymer measured at 190 ° C. under a load of 6 kg / cm ² .

The ethylene content in the ethylene copolymer is
^{It was determined from a 13} C-NMR dyad sequence. The molecular weight distribution was measured by GPC using polystyrene as a standard.
(Waters 150CV type, o-dichlorobenzene solvent, column SHOdex, temperature 145 ° C, concentration
(0.05% by weight) and the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn.

Reference Example 1 (Synthesis of organosilicon compound component) A stirrer piece was placed in a 200 ml three-necked flask equipped with a dropping funnel. Distilled and dehydrated n-heptane 100m
l, 17.9 ml of decahydroisoquinoline (0.12 m
ol) 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, the stirrer piece was put into a flask with a glass filter (capacity: 400 ml) equipped with a dropping funnel, and the inside of the flask was sufficiently purged with nitrogen using a vacuum pump. -Heptane 6
0 ml, tetramethoxysilane 8.9 ml (0.06 m
ol), 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 dropping, continue at 40 ° C
For 2 hours and further at room temperature for 12 hours. After confirming that the target product was produced by gas chromatography, the precipitate was filtered. The solvent in the filtrate is sufficiently distilled off under reduced pressure, and then the product is purified by primary and secondary distillation to obtain the desired product, bis (perhydroisoquinolino) dimethoxysilane. Was. This compound had a boiling point of 179.3 ° C./1 mmHg and a GC purity of 98.0%.

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
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, and the temperature of the reaction solution was kept in 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 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 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 are added, and 90
The reaction was performed at a temperature of 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 catalyst solid component was 2.32% by weight.
This solid was suspended in 80 ml of heptane to prepare a heptane slurry of a catalyst solid component.

(2) Copolymerization of Ethylene and Propylene A glass ampoule in which an n-heptane slurry (8 mg as a solid catalyst component) of the solid catalyst component (A) is sealed in a stainless steel autoclave having a 2 L internal volume equipped with a stirrer. After the tube was attached, the inside of the autoclave was sufficiently replaced with nitrogen. Next, 900 ml of n-heptane, component [B]
2.1 ml of n-heptane solution containing 2.1 mmol of triethylaluminum as the component [C] and 0.35 of bis (perhydroisoquinolino) dimethoxysilane as the component [C]
1.74 ml of a mmol-containing n-heptane solution were charged. Subsequently, after introducing 0.5 MPa of hydrogen, 300 ml of liquefied propylene and 1.5 MPa of ethylene, the inside of the autoclave was brought to 10 ° C., stirring was started, and the glass ampule was crushed and prepolymerized for 10 minutes. Subsequently, the temperature inside the autoclave was raised to 60 ° C., ethylene was continuously supplied, and copolymerization was carried out for 60 minutes while maintaining the ethylene pressure at 1.5 MPa. After completion of the copolymerization, unreacted ethylene and propylene gas are released, ethanol containing HCl is added, and the precipitated amorphous polymer is dried under reduced pressure at 70 ° C. for 20 hours to obtain a white rubbery ethylene copolymer. Was. Table 1 shows the measurement results of the polymerization activity and the properties of the polymer.

Example 2 Ethylene was copolymerized in the same manner as in Example 1 except that the ethylene pressure was changed to 1 MPa. Table 1 shows the measurement results of the polymerization activity and the properties of the polymer.

Example 3 Copolymerization of ethylene was carried out in the same manner as in Example 1 except that the ethylene pressure was changed to 0.5 MPa. Table 1 shows the measurement results of the polymerization activity and the properties of the polymer.

Example 4 Prepolymerization with ethylene: 800 ml of heptane was added into a 2 L stainless steel autoclave equipped with a stirrer, and tri-n-octyl aluminum 1 was used as a component [B].
0.0 mmol, the catalyst solid component (2.5 mmol in Ti) described in Example 1 as the component [A], and 0.10 mmol of bis (perhydroisoquinolino) dimethoxysilane as the component [C] were added. Next, after introducing 0.15 MPa of hydrogen, the content of the autoclave was heated to 60 ° C., and ethylene was fed at 0.93 L / min. For 2 hours to obtain a prepolymer containing 0.020 mmol of Ti atoms per gram of solid catalyst.

Ethylene gas phase copolymerization: 500 g of a polyethylene powder prepared in advance was placed in a stirred gas phase polymerization reactor having a diameter of 20 cm and a length of 50 cm, and ethylene / 1 containing triethylaluminum was stirred from the bottom while stirring the powder at 300 rpm. 4-butene / hydrogen (1/3 / 1.2 molar ratio)
The mixed gas at 5 ° C was raised at a rate of 20 cm ³ / sec and circulated. For the polymerization, the prepolymer was introduced at a rate of 10 g / hour, the polymerization temperature was 75 to 85 ° C., and the polymerization pressure was 0.2 MPa.
a, Continuously performed at an Al / Ti atomic ratio of 10 for 10 hours.
Table 2 shows the measurement results of the polymerization activity and the properties of the polymer.
Shown in

Example 5 In Example 4, ethylene / 1-butene / hydrogen (1/1)
(6 / 1.2 molar ratio), except that the gas phase copolymerization of ethylene was carried out in the same manner. Table 2 shows the measurement results of the polymerization activity and the properties of the polymer.

Example 6 In Example 4, ethylene / 1-hexene / hydrogen (1
/3/1.2 mol ratio), except that the gas phase copolymerization of ethylene was carried out in the same manner. Table 2 shows the measurement results of the polymerization activity and the properties of the polymer.

Comparative Example 1 Ethylene was copolymerized in the same manner as in Example 1 except that no organosilicon compound was used in the copolymerization. Table 1 shows the measurement results of the polymerization activity and the properties of the polymer.

Comparative Example 2 Ethylene gas phase copolymerization was carried out in the same manner as in Example 4 except that no organosilicon compound was used in the copolymerization. Table 2 shows the measurement results of the polymerization activity and the properties of the polymer.

[0117]

[Table 1]

[0118]

[Table 2]

[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.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A BA02A BA02B BA03A BB00A BB01B BC06A BC15B BC25B BC34A BC39B CA18A CA19A CB27A CB44A DB03A DB04A DB05A EC02 FA01 FA02 GA04 GA03 AA16Q AA17Q AA19Q AR17R AR18R AR22R AS11R AS15R BC27R CA04 CA05 DA04 FA09

Claims (2)

[Claims] 1. [A] a solid catalyst component essentially containing magnesium, titanium and a halogen element, [B] an organoaluminum compound component, and [C] an organosilicon represented by the general formula (1) or (2) In the presence of a catalyst comprising a compound component, ethylene and α-olefin are copolymerized,
A method for producing an ethylene copolymer, comprising producing an ethylene copolymer having an ethylene content of 11 to 95% by weight. (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 24 carbon atoms.
Hydrocarbon group, a hydrocarbon alkoxy group hydrocarbon amino group or 1 to 24 carbon atoms having 2 to 24 carbon atoms, R ³
N has 7 to 40 carbon atoms forming a skeleton together with a nitrogen atom.
Represents a polycyclic amino group of the formula) Embedded image 2. A catalyst solid component essentially comprising [A] magnesium, titanium, a halogen element and an organosilicon compound represented by the general formula (1) or (2); and [B] an organoaluminum compound component. A method for producing an ethylene copolymer, characterized in that ethylene and an α-olefin are copolymerized in the presence of a catalyst to produce an ethylene copolymer having an ethylene content of 11 to 95% by weight. (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 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or Carbon number 1
And R ³ N represents a polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom. Embedded image