JP2000186109A - Production of polypropylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene having a high stereoregularity of polymer, a wide molecular weight distribution, a high rigidity of molded product and slight generation of gel in high polymerization activity by polymerizing propylene by using a catalyst comprising a catalytic solid component, an organoaluminum compound component and an organosilicon compound component. SOLUTION: Propylene is polymerized by using a catalyst comprising (A) a catalytic solid component essentially composed of magnesium, titanium, a halogen element and an electron donor, (B) an organoaluminum compound component and (C) an organosilicon compound to give a polypropylene. The polymerization is a multistage continuous polymerization constituted of a polymerization process in which the component C is an organosilicon compound of the formula (NR1)2Si(OR2)2 (R1N a 7-40C saturated polycyclic amino forming a skeleton with nitrogen; R2 is a 1-8C hydrocarbon) and a polymerization process in which the component C is a compound containing no nitrogen-silicon bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer having a high stereoregularity, a wide molecular weight distribution, good moldability,
In particular, the present invention relates to a method for producing polypropylene having a low gel content in a molded article.

[0002]

2. Description of the Related Art In recent years, in order to polymerize propylene, a solid catalyst component essentially containing magnesium, titanium, a halogen element, and an electron donor, an organometallic compound component of a Group 1 to 3 metal in the periodic table, and an electron donor. A supported high-activity catalyst system comprising an organosilicon compound component, which is a solid, is widely known.

A propylene polymer obtained by using the above-mentioned supported catalyst system usually has a narrow molecular weight distribution and a small viscoelasticity when the polymer is melted, and causes problems in moldability, molding appearance and the like depending on the use. There are cases. In order to improve this problem, means for expanding the molecular weight distribution by a multi-stage polymerization method using a plurality of polymerization vessels has been adopted. In this case, in order to produce a polymer having a broader molecular weight distribution, a complicated operation is required, and the production speed must be lowered industrially, which is not preferable from the viewpoint 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 reactors, it is necessary to use a chain transfer agent such as hydrogen excessively in one reactor to produce a low molecular weight polymer. Not
There is a problem that affects the production speed.

Japanese Patent Application Laid-Open Nos. Hei 3-7703 and Hei 4-136006 disclose a polymerization method in which at least two types of third components that give different MFRs are mixed and used. In many cases, one of the third components acts, and the effect of expanding the molecular weight distribution is small. In addition, since it is essential to use two or more types of third components, the polymerization process, the polymerization apparatus, and the polymerization operation become more complicated.

Japanese Patent Application Laid-Open No. H08-120021 discloses a method in which a methyl cyclic aminosilane compound is used as a third component, and Japanese Patent Application Laid-Open No. H08-143621 specifically uses a cyclic aminosilane compound as a third component. Although the method used is disclosed, there is a problem that the molecular weight distribution is not necessarily wide in these specifically described compounds.

On the other hand, a propylene polymer having a wide molecular weight distribution and high crystallinity can be obtained by previously producing a high-crystallinity low-molecular-weight propylene polymer and a high-crystalline high-molecular-weight propylene polymer by a conventional method. However, a method of melt-mixing them is conceivable, but in this case, if a propylene polymer having a relatively low molecular weight and a wide molecular weight distribution is to be produced, a propylene polymer having a considerably low molecular weight and a propylene polymer having a high molecular weight are produced. It is very difficult to mix uniformly, and the formation of a gel based on poor dispersion of a high molecular weight substance becomes a problem.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a high polymerization activity, a high stereoregularity of the polymer, a wide molecular weight distribution and a high rigidity of the molded body. It is an object of the present invention to provide a method for producing a propylene polymer which is high and generates less gel.

[0008]

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] an organosilicon compound. In a method for producing polypropylene, wherein propylene is polymerized using a catalyst comprising a compound component, the component [C] is a compound represented by the general formula (NR ¹ ) ₂ S
Organosilicon compound (C-1) represented by i (OR ² ) ₂
And a multistage continuous polymerization comprising a polymerization step in which the component [C] is an organosilicon compound (C-2) having no nitrogen-silicon bond. (However, in the general formula (C-1), R ¹ N represents a saturated polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom, and R ² represents a C 1 to C 8 amino group. Represents a hydrocarbon group.)

The present invention discloses a method for producing a propylene polymer having a wide molecular weight distribution by polymerizing propylene in two or more multistage continuous polymerization steps using a specific [C] organosilicon compound component. In one polymerization step, [C] an organosilicon compound component represented by the general formula (NR ¹ ) ₂ Si (O
Using the organosilicon compound (C-1) represented by R ² ) ₂ , the weight average molecular weight (Mw) is 20 in terms of polystyrene.
Produces more than 000 polypropylene components. In another polymerization step, [C] an organosilicon compound having no nitrogen-silicon bond (C-
Using 2), the weight average molecular weight (Mw) is 200,00
Produces less than 0 polypropylene component.

[0010] Each of these two polymerization steps may comprise two or more stages of polymerization reactions.
The production of polypropylene in a two-stage polymerization step, each of which is a minimum one-stage polymerization reaction, is excellent in terms of production operation and cost.

In the present invention, the method for producing the solid catalyst component (A) is not particularly limited.
590, 56-55405, 56-4
Nos. 5909, 56-163102, 57
JP-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, and JP-A-60-32805
JP-A-61-18330 and JP-A-61-5510
No. 4, JP-A-2-77413, 2-117
For example, a method proposed in Japanese Patent Publication No. 905 or the like can be adopted.
As a typical production method, (1) a method of co-milling a magnesium compound such as magnesium chloride, an electron donor, and a titanium halide compound such as TiCl4, (2) dissolving the magnesium compound and the electron donor in a solvent, A method of adding a titanium halide compound to this solution to precipitate a catalyst solid and the like can be mentioned.

As the component [A], JP-A-60-152
No. 511, No. 61-31402, No. 62-8
The catalyst solid component described in 1405 is particularly preferred for achieving the effects of the present invention. According to these production methods, a solid is deposited by reacting an aluminum halide with a silicon compound and further reacting a Grignard compound. As the aluminum halide that can be used in the above reaction, anhydrous aluminum halide is preferable, but it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water is also used. Can be. Specific examples of aluminum halide include aluminum trichloride, aluminum tribromide, and aluminum triiodide, and aluminum trichloride is particularly preferable.

Specific examples of the silicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane, 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 determined by the element ratio (Al / Si)
Usually 0.4 to 1.5, preferably 0.7 to 1.3
It is preferable to use an inert solvent such as hexane or toluene for the reaction. 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 0.1 to 5 hours.
5 to 3 hours.

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

The amount of the magnesium compound to be used is usually 0.5 to 3, preferably 1, in terms of an element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound. 5
To 2.3. The reaction temperature is usually -50 to 1
00 ° C, preferably -20 to 50 ° C, and the reaction time is usually 0.2 to 5 hours, preferably 0.5 to 3 hours.

The white solid obtained in the reaction of the aluminum halide with the silicon compound and subsequently with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. As a method of contact treatment,
(1) a method in which a solid is treated with a titanium halide compound, then treated with an electron donor, and further treated with a titanium halide compound, and (2) the solid is 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 can be generally 50 to 150 ° C., and the contact time is not particularly limited, but can be generally 0.2 to 5 hours. Also,
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.

As the electron donor used in the above-mentioned contact treatment, an aromatic ester, particularly, an orthophthalic diester is preferable. 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.

After the above-mentioned contact treatment, generally, the treated solid is 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 a propylene polymerization catalyst. can do.

As the organoaluminum compound as the component [B] of the present invention, alkylaluminum, halogenoalkylaluminum and the like can be used, but alkylaluminum is preferable. Particularly preferred are trialkylaluminums, and specific examples include trimethylaluminum, triethylaluminum, tripropylaluminum, 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 used as the propylene polymerization catalyst is 1 to 1000, preferably 3 to 500, in terms of the element ratio (Al / Ti) of titanium in the solid catalyst component [A] to titanium.

In the component [C] of the present invention, [C-1]
An organosilicon compound represented by the general formula (NR ¹ ) ₂ Si (OR ² ) ₂ . (However, in the above general formula [C-1], R ¹ N represents a saturated polycyclic amino group having 7 to 40 carbon atoms forming a skeleton together with a nitrogen atom, and R ² represents a C 1 to C 8 amino group. Represents a hydrocarbon group.)

In (NR ¹ ) ₂ Si (OR ² ) ₂ , 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 HNR ¹ is removed to form a chemical bond between Si and N. The two NR ¹ groups may each be the same or different.

As a specific example of R ² NH, as shown by the following chemical structural formula,

[0027]

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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.

Particularly preferred amine compounds include
Hydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline and derivatives thereof can be mentioned.

R ² is a hydrocarbon group having 1 to 8 carbon atoms,
Examples thereof include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. Specific examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, ter-butyl, sec-butyl, n-pentyl, and iso-pentyl. , Cyclopentyl group, n-hexyl group, cyclohexyl group and the like. Particularly preferred is a methyl group.

Further, [C-1] the general formula (NR ¹ ) ₂ Si
Examples of the organosilicon compound represented by (OR ² ) ₂ include a perhydroquinolino compound represented by the general formula (1), a perhydroisoquinolino compound represented by the general formula (2), and a general formula (3) )) (Per-hydroquinolino) (per-hydroisoquinoli) compound and the like.

[0032]

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R ³ represents a substituent on the saturated ring of R ¹ N;
It is hydrogen or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred as R ³ 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 ¹ N may be one or more.

As the compound represented by the general formula (1),
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, (perhydroquinolino) (2-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (3-methylpa-hydroquinolino) dimethoxysilane, (perhydroquinolino) (4-methylpara-
(Hydroquinolino) dimethoxysilane, (per-hydroquinolino) (5-methylper-hydroquinolino) dimethoxysilane, (per-hydroquinolino) (6-methylpa-hydroquinolino) dimethoxysilane, (per-hydroquinolino)
(7-methylperhydroquinolino) dimethoxysilane,
(Perhydroquinolino) (8-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (9-
Methyl perhydroquinolino) dimethoxysilane,
Hydroquinolino) (10-methylpa-hydroquinolino)
Examples include compounds such as dimethoxysilane.

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

As the compound represented by the general formula (2),
Bis (perhydroisoquinolino) dimethoxysilane; and the like.

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

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

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 (3),
(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.

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

[C-1] Formula (NR ¹ ) ₂ Si (O
Specific examples of the organosilicon compound represented by R ² ) ₂ include compounds represented by the following chemical structural formulas.

[0049]

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[0050]

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The component [C-2] of the present invention is a silane compound having no nitrogen-silicon bond (N-Si), such as dialkyldialkoxysilane, cycloalkylalkyldialkoxysilane, dicycloalkyldialkoxysilane, Alkoxysilane compounds such as alkyltrialkoxysilanes and cycloalkyltrialkoxysilanes. Preferred alkoxysilane compounds are dialkoxysilane compounds such as dialkyldialkoxysilane, cycloalkylalkyldialkoxysilane, dicycloalkyldialkoxysilane, and particularly preferred are dialkyldimethoxysilane, cycloalkylalkyldimethoxysilane, and dialkyldimethoxysilane. Dimethoxysilane compounds such as cycloalkyldimethoxysilane.

Specific compounds include cyclopentyl (methyl) dimethoxysilane, cyclopentyl (ethyl) dimethoxysilane, cyclohexyl (methyl) dimethoxysilane, cyclohexyl (ethyl) dimethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane and isopropyl (ethyl) Dimethoxysilane, diisobutyldimethoxysilane, isobutyl (ethyl) dimethoxysilane, disec-butyldimethoxysilane, sec-butyl (methyl) dimethoxysilane, sec-butyl (ethyl) dimethoxysilane, t
er-butyl (methyl) dimethoxysilane, ter-butyl (ethyl) dimethoxysilane, texyltrimethoxysilane, and the like.

In the present invention, as the component [A], a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and components [C-1] [C- Propylene polymer can be produced by polymerizing propylene in at least two or more multi-stage polymerization vessels in the presence of the different organosilicon compounds of 2). When [C-1] is used alone as an external electron donor, a polypropylene having a wide molecular weight distribution can be produced, and when [C-2] is used alone as an external electron donor, the molecular weight distribution is narrow. Polypropylene can be manufactured.

In the present invention, the order of the polymerization steps using each of the components [C-1] and [C-2] is not limited,
In the presence of [C-1], the amount of hydrogen added as a chain transfer agent is controlled, and the molecular weight distribution is wide in one or more multi-stage polymerization vessels,
A high molecular weight polypropylene having a weight average molecular weight of 200,000 or more in terms of polystyrene is produced, and then [C-2]
In the presence of (1), a process of producing a low molecular weight polypropylene having a narrow molecular weight distribution and a weight average molecular weight of less than 200,000 by controlling the amount of hydrogen in a one-stage or more multistage polymerization vessel is preferred. It is operationally advantageous to gradually increase the amount of hydrogen in the polymerization system. In particular, it is particularly preferable in terms of operation to produce a high molecular weight polypropylene in a single step in the presence of [C-1] and then produce a low molecular weight polypropylene in a single step in the presence of [C-2]. .

The amounts of the components [C-1] and [C-2] used are as follows:
Component [B] elemental ratio of silane to aluminum (S
i / Al) is preferably 0.01 to 1.0, and particularly preferably 0.05 to 0.33.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used to produce a propylene polymer having the desired stereoregularity and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions, but is usually from 0.05 to 3.0 hydrogen partial pressure. Range.

In the present invention, the order of contact of the respective catalyst components during the polymerization of propylene is not particularly limited, but the components [A], [B] and [C], or the components [B] and [C] may be used. Is preferably brought into contact with the component [A] beforehand.

In the present invention, in addition to propylene, a small amount of ethylene and other α-olefins are used in order to lower the melting point or increase the transparency of the film as long as the properties of the present invention are not impaired.
Also included is the production of polypropylene polymers that copolymerize with olefins such as 1-butene, 1-hexene, 4-methylpentene-1, 1-octene, and the like. In addition, production of a so-called propylene block copolymer in which propylene is further polymerized and then copolymerized with another olefin such as ethylene is also included.

The polymerization method in the present invention includes a slurry polymerization method using a non-polar solvent such as propane, butane, pentane, hexane, heptane and octane, and a polymerization method in which a monomer is brought into contact with a catalyst in a gaseous state. A phase polymerization method, a bulk polymerization method in which a monomer in a liquefied state is polymerized in a solvent, and the like can be employed. In the above polymerization method,
Either continuous polymerization or batch polymerization may be performed. The polymerization pressure is 0.1 to 20 MPa, preferably 1 to 6 MPa
a, the polymerization temperature is 60 ° C. or higher, preferably 65 to 100
° C, more preferably 70 to 90 ° C. The polymerization time is usually in the range from 0.1 to 10 hours, preferably from 0.5 to 7 hours. The catalyst system has particularly high catalytic activity at a high polymerization temperature, and the obtained propylene polymer has a high stereoregularity and a wide molecular weight distribution.

In the present invention, it is preferable that ethylene, propylene or another α-olefin is preliminarily polymerized according to the various polymerization methods described above, and then the propylene main polymerization is carried out using the prepolymerized solid as a catalyst. The effects of the prepolymerization include an improvement in polymerization activity, an improvement in stereoregularity of the polymer, and a stabilization of the particle shape of the polymer. The prepolymerization method may be performed in the presence of the catalyst solid component [A], the organoaluminum compound component [B] and the silane compound component [C], or the catalyst solid component [A] instead of the catalyst solid component [A]. The prepolymerized solid is obtained by contacting with the aluminum compound component [B] and the silane compound component [C], and polymerizing a limited amount of ethylene or α-olefin using the pretreated solid obtained by washing the solid. Can be prepared. In the present invention,
It is preferable to use [C-1] as [C].

In the present invention, when the above-mentioned pretreated solid or prepolymerized solid is used as a catalyst solid component in the main polymerization, one or more stages of the main polymerization can be carried out without using the silane compound component [C] in the main polymerization. After that, polypropylene can be produced by one or more stages of polymerization using the silane silane compound component [C] not used in the prepolymerization or pretreatment. [C-1] is used in the prepolymerization or pretreatment, and the main polymerization is performed in one or more stages with or without the addition of [C-1].
It is preferable to add 2) and perform main polymerization in one or more stages to produce polypropylene.

As the pretreatment of the present invention, the components [A],
The component [B] and the component [C] are mixed, and usually 0 to 10
React at 0 ° 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 main polymerization.

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 the catalyst residue increases, and the stereoregularity of the propylene polymer is not sufficient. If it exceeds 100 g, the polymerization activity and the crystallinity of the propylene polymer tend to decrease. The prepolymerization temperature is from 0 to 100 ° C, preferably from 10 to 90 ° 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 decreases in the main polymerization or the crystallinity of the obtained propylene polymer decreases. I do.

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

The polypropylene which can be produced in the present invention has a ratio Mw / Mn of the weight average molecular weight to the number average molecular weight in terms of polystyrene measured by GPC of 10 or more, more preferably 15 or more, particularly preferably 20 or more. A propylene polymer having a methyl group pentad fraction of 92% or more, more preferably 94% or more, particularly preferably 97% or more in the arrangement of methyl groups in the propylene monomer unit (where dd or 11 is m) is used. The melting point measured at a heating rate of 10 ° C. per minute is 16
The temperature is 0 ° C or higher, more preferably 162 ° C or higher, and particularly preferably 164 ° C or higher.

The propylene polymer of the present invention is highly crystalline,
Moreover, since the molecular weight distribution is wide, the gel of the molded product is small, the mechanical properties such as rigidity and tensile strength are excellent, and the fluidity is high, the molding speed can be increased. For this reason, the propylene polymer of the present invention is not particularly limited, but can exhibit excellent performance as a structural material for automobiles and home appliances. In addition to using the propylene polymer of the present invention alone, blends with many other plastics and elastomers, as well as inorganic and organic fillers such as glass fibers, and crystal nucleating agents can be mixed and used.

[0068]

According to the present invention, when propylene is polymerized, the polymerization activity is high, the stereoregularity of the polymer is high, the molecular weight distribution is wide, the rigidity of the molded product is high, and the generation of gel is small. Propylene polymers can be produced.

[0069]

Embodiments of the present invention will be described below. In an embodiment,

"Polymerization activity" is the yield (g) of polymer produced per gram of solid catalyst. MFR is AST
Polymer melt index (g / 10 m) measured at 190 ° C. under a load of 2.16 kg / cm ² according to MD-1238.
in. ). One of the indicators of the tacticity of a polymer,
Its microtacticity - iso pentad fraction was examined (mmmm) is 1975 Macromolecules, Vol. 8, ¹³ C, which was assigned on the basis of 687 pages
-Calculated from the peak intensity ratio of the NMR spectrum. ¹³ C
-The 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 a GPC (Waters 150CV type, ozone) using polystyrene as a standard substance.
-Dichlorobenzene solvent, column SHOdex, temperature 1
(45 ° C., concentration 0.05 wt%), and the weight average molecular weight (Mw) and the number average molecular weight (Mn) ratio Mw / Mn were evaluated.

The number of gels was counted within 450 cm ^{2 of} a film obtained by T-die molding polypropylene.

Example 1 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride was added to 40 ml of toluene.
Then, 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, and the temperature of the reaction solution was in the range of −5 to 0 ° C. Kept inside.
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
The suspension was added with 150 mmol of titanium tetrachloride and 3.3 mmol of di-n-heptyl phthalate, and reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off and washed with toluene and then with n-heptane. Further, the solid was suspended again in 30 ml of toluene,
150 mmol of titanium tetrachloride was added, and the mixture was stirred at 90 ° C.
For 1 hour. At the same temperature, the solid was filtered off, and the solid was washed with toluene and then with n-heptane. The titanium content in the obtained catalyst solid component was 3.55 wt%. This solid was suspended in 80 ml of heptane, and n-
A heptane slurry was prepared.

(2) Polymerization of Propylene A glass ampoule tube in which n-heptane slurry (8 mg as a solid catalyst component) is sealed in a 2 L stainless steel autoclave equipped with a stirrer is attached. After that, the inside of the autoclave was sufficiently replaced with nitrogen. next,
2.1 ml of an n-heptane solution containing 2.1 mmol of triethylaluminum and 1.74 ml of an n-heptane solution containing 0.35 mmol of bis (perhydroisoquinolino) dimethoxysilane as a component [C-1] were charged. . Subsequently, after introducing 0.05 MPa of hydrogen, 1.2 L of liquefied propylene was introduced and the autoclave was shaken. The autoclave was cooled to 10 ° C., and at the same time as the stirring was started, the glass ampoule tube containing the solid catalyst component was crushed.
Prepolymerization was performed for 0 minutes. Continue in the autoclave 70
C., and the first-stage polymerization was performed at 70.degree. C. for 1 hour. Unreacted propylene gas is released, and under nitrogen flow, 1.74 n-heptane solution further containing 0.35 mmol of diisopropyldimethoxysilane as a component [C-2].
ml. Subsequently, after introducing 0.4 MPa of hydrogen, 1.2 L of liquefied propylene was introduced, the inside of the autoclave was heated to 70 ° C, and the second-stage polymerization was further performed at 70 ° C for 1 hour. The polymer was dried under reduced pressure at 50 ° C. for 20 hours,
A white powdery polypropylene was obtained. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Examples 2 to 3 The same procedures as in Example 1 were carried out except that the organosilicon compounds shown in Table 1 were used as the component [C-2]. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Example 4 The procedure of Example 1 was repeated, except that the hydrogen was changed to 0.02 MPa in the first-stage polymerization. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Example 5 The procedure of Example 1 was repeated, except that the polymerization time was changed to 30 minutes in the first-stage polymerization. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Example 6 The procedure of Example 1 was repeated except that the polymerization time was changed to 30 minutes in the second stage polymerization. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Example 7 The procedure of Example 1 was repeated except that the hydrogen was changed to 0.6 MPa in the second stage polymerization. Table 1 shows the results of the polymerization activity and the properties of the polymer.

Comparative Example 1 An ampoule made of glass in which n-heptane slurry (8 mg as a solid catalyst component) of the solid catalyst component prepared in Example 1 was sealed in a stainless steel autoclave having an inner volume of 2 L equipped with a stirrer. After the tube was attached, the inside of the autoclave was sufficiently replaced with nitrogen. Next, 2.1 ml of an n-heptane solution containing 2.1 mmol of triethylaluminum, [C-1]
N-heptane solution containing 0.35 mmol of bis (perhydroisoquinolino) dimethoxysilane as a component
74 ml were charged. Subsequently, after introducing 0.05 MPa of hydrogen, 1.2 L of liquefied propylene was introduced and the autoclave was shaken. Cool the autoclave to 10 ° C,
With the start of stirring, the glass ampule tube containing the solid catalyst component was crushed and preliminarily polymerized for 10 minutes. Subsequently, the inside of the autoclave was heated to 70 ° C., and polymerization was carried out at 70 ° C. for 1 hour. Next, a glass ampoule tube enclosing n-heptane slurry (8 mg as a solid catalyst component) as a catalyst solid component was attached to a stainless steel autoclave having an inner volume of 2 L with a stirrer. -The inside of the tube was sufficiently replaced with nitrogen. Next, 2.1 ml of an n-heptane solution containing 2.1 mmol of triethylaluminum and 1.74 ml of an n-heptane solution containing 0.35 mmol of diisopropyldimethoxysilane as a component [C-2] were charged. Subsequently, after introducing 0.4 MPa of hydrogen, 1.2 L of liquefied propylene was introduced and the autoclave was shaken.
The autoclave was cooled to 10 ° C., and at the same time as the stirring was started, the glass ampule tube containing the solid catalyst component was crushed and prepolymerized for 10 minutes. Subsequently, the inside of the autoclave was heated to 70 ° C., and polymerization was carried out at 70 ° C. for 1 hour. [C-
The polymer obtained using the [1] component and the polymer obtained using the [C-2] component were blended at 230 ° C. using a single-screw (diameter 65 mm) extruder. The results on the properties of the blend are shown in Table 1.

Comparative Example 2 The procedure of Comparative Example 1 was repeated, except that the charged hydrogen was changed to 0.02 MPa during the polymerization using the component [C-1].
Table 1 shows the results of the characteristics.

[0082]

[Table 1]

[Brief description of the drawings]

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

Continuing on the front page F-term (reference) 4J011 AA05 AA07 AC03 4J028 AA01A AB01A AC04A AC05A AC06A BA01A BA03B BB01A BC06A BC15B BC25B BC34A BC34B BC39B CA18A CA19A CA20A CB44A DB03A DB04A DB05 FA01 GA01 FA05

Claims (1)

[Claims] 1. A catalyst comprising [A] a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] an organosilicon compound component. In the method for producing polypropylene, wherein the component [C] is an organosilicon compound (C-1) represented by the general formula (NR ¹ ) ₂ Si (OR ² ) _2; ]
An organosilicon compound whose component does not have a nitrogen-silicon bond (C
-2) a method for producing polypropylene, which is a multi-stage continuous polymerization comprising a polymerization step. (However, in the general formula (C-1), R ¹ N represents a saturated polycyclic amino group having 7 to 40 carbon atoms which forms a skeleton together with a nitrogen atom, and R ² represents a C 1 to C 8 amino group. Represents a hydrocarbon group.)