JP2000017009A - Preparation of propylene block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having a high stereoregularity and a wide molecular weight distribution and enable the control of the molecular weight by conducting copolymerization with a catalyst containing an organosilicon compound having a specific cis/trans ratio of a polycyclic amino group portion. SOLUTION: A solid catalyst component containing Mg, Ti, a halogen and an electron donor as essential components, an organoaluminum compound and an organosilicon compound of formula I or II (wherein R1 is a 1-8C hydrocarbon group; R2 is a 2-24 hydrocarbon group, a 2-24C hydrocarbon amino group or a 1-24C hydrocarbon alkoxy group; and R3N is a 7C or higher polycyclic amino forming a skeleton together with a nitrogen atom) with a cis/trans ratio of the polycyclic amino group of 90/10-0/100 are combined to obtain a catalyst. In the presence of this catalyst, propylene is (co)polymerized alone or together with 1-40 wt.% of another α-olefin at a pressure of ambient pressure to 20 kg/cm2 at 30-90 deg.C for 5 minutes to 5 hours to obtain a propylene block copolymer having a molecular weight distribution of 15-50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a propylene block copolymer having high stereoregularity, a wide molecular weight distribution, and capable of appropriately controlling the molecular weight.

[0002]

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

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

A method for producing a propylene block copolymer usually comprises a first stage of polymerization in liquid propylene and a second stage of a copolymerization process. A so-called supported catalyst used as a polymerization catalyst generally has a high activity at an early stage, but has a poor activity persistence and has a problem that a copolymerization activity in a subsequent stage is low.

As a method of increasing the copolymerization activity in the latter stage, for example, a method of adjusting polymerization conditions such as polymerization time, polymerization temperature and polymerization pressure between the former stage and the latter stage has been attempted. However, in these methods, although the polymerization activity in the latter stage relatively increases, the catalyst activity as a whole, the stereoregularity of the copolymer decreases, or the molecular weight of the rubber component generated by copolymerization decreases, and ethylene decreases. There is a problem that the content is reduced, and there is a problem that the effect of improving the rigidity and impact resistance of the obtained propylene block copolymer is reduced.

[0006] The propylene polymer obtained using the supported catalyst system usually has a narrow molecular weight distribution and a small viscoelasticity when the polymer is melted. It may be. To solve this problem, Japanese Patent Application Laid-Open No. 63-245408,
No. 32207, JP-A-4-370103 and the like disclose a method of expanding the molecular weight distribution by polymerization using a plurality of polymerization vessels or multi-stage polymerization. However, such a method requires a complicated operation and has to reduce the production speed industrially, which is not preferable in view of cost. Furthermore, in order to produce a propylene polymer having a low molecular weight and a wide molecular weight distribution in a plurality of polymerization vessels, one of the polymerization vessels must produce an excess of a chain transfer agent such as hydrogen to produce a low molecular weight polymer. In the case of a polymerization reactor having a pressure resistance limit, the polymerization temperature must be lowered, and there is a problem that the production speed is adversely affected.

Further, JP-A-3-7703, JP-A-4-136006, and JP-A-8-30192 disclose polymerization using at least two kinds of organosilicon compounds which give different MFRs as a catalyst component. Although a method is disclosed, either one of the catalyst components often acts, and the effect of expanding the molecular weight distribution is not sufficient. Further, in this method, it is essential to use two or more types of catalyst components, so that the polymerization process, the polymerization apparatus, and the polymerization operation become more complicated.

Further, Japanese Patent Application Laid-Open Nos. H08-120021, H08-143621, H08-231663
In Japanese Patent Application Laid-Open Publication No. H11-163, a method using a cyclic aminosilane compound is disclosed, but there is a problem that the molecular weight distribution is not necessarily wide in these specifically described compounds.

Further, JP-A-6-25336, JP-A-7-90012, and JP-A-7-97411 disclose nitrogen in which an arbitrary carbon atom in a heterocycle is directly bonded to a silicon atom. A method using an atom-containing heterocyclic-substituted organosilicon compound is disclosed, but the molecular weight distribution is not described.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has a wide molecular weight distribution while maintaining high stereoregularity and high melting point, and has a high molecular weight in the copolymer. An object of the present invention is to provide a method for producing a propylene block copolymer having a high ethylene content in a rubber component while appropriately controlling the molecular weight.

[0011]

According to the present invention, there are provided [A] a catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] a general formula (1) ) Or (a) by polymerizing propylene or propylene with another α-olefin in the presence of a catalyst comprising the organosilicon compound component represented by (2), to obtain a propylene polymer having an α-olefin content of 10% by weight or less. (B) Propylene and other α
Polymerizing olefin with α-olefin content of 10
In the method for producing a propylene block copolymer produced by a step of producing a propylene polymer of from 40 to 40% by weight, the cis / trans ratio of the polycyclic amino group portion of the organosilicon compound component of [C] is 90/10 To 0/100, which relates to a method for producing a propylene block copolymer.

[0012]

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[0013]

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

Further, the present invention provides a method for carrying out the polymerization of propylene or propylene with another α-olefin in the presence of a catalyst comprising the above-mentioned [A], [B] and [C]. The present invention relates to a method for producing a propylene block copolymer, wherein a gas phase copolymerization of propylene and another α-olefin is carried out in a second stage without deactivating the propylene block copolymer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor is used as the component [A]. The method for producing the solid catalyst component of the component [A] is not particularly limited, and examples thereof include JP-A-54-94590 and JP-A-56-55405.
JP, JP-A-56-45909, JP-A-56-45909
No. 163102, JP-A-57-63310,
JP-A-57-115408, JP-A-58-830
No. 06, JP-A-58-83016, JP-A-58-83016
JP-A-8-138707, JP-A-59-149905, JP-A-60-23404, JP-A-60-3
The methods proposed in JP 2805, JP-A-61-18330, JP-A-61-55104, JP-A-2-77413, JP-A-2-117905 and the like can be used.

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

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

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

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 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 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 usable for the contact treatment include tetrachlorotitanium, tetrabromotitanium, trichloromonobutoxytitanium, tribromomonoethoxytitanium, trichloromonoisopropoxytitanium, dichlorodiethoxytitanium, dichlorodiethoxytitanium and the like. Butoxytitanium, monochlorotriethoxytitanium and monochlorotributoxytitanium can be mentioned. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferred.

The electron donor used in the contact treatment is a Lewis basic compound, preferably an aromatic diester, particularly preferably an orthophthalic diester. Specific examples of the orthophthalic diester include diethyl orthophthalate, di-n-butyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, di-n-hexyl orthophthalate, di-2-ethylhexyl orthophthalate, and di-n-orthophthalate.
Heptyl, di-n-octyl orthophthalate and the like can be mentioned. Further, as the electron donor, two or more ether groups as disclosed in JP-A-3-706, JP-A-3-62805, JP-A-4-270705, and JP-A-6-25332 are used. Compounds having the formula (I) can also be preferably used.

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 converted to α-α as the catalytic solid component [A] of the present invention.
It can be used as an olefin polymerization catalyst.

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. Specific examples thereof include trimethylaluminum and triethylaluminum , Tri-n-propylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like. Any of the above-mentioned organoaluminum compounds can be used as a mixture. Further, a polyaluminoxane obtained by a reaction between an alkyl aluminum and water can be used in the same manner.

The amount of the component [B] used as the polymerization catalyst for the α-olefin is determined by the element ratio (Al / Al) of the component [B] to the titanium (Ti) of the component [A].
Ti), 0.1 to 500, preferably 0.5 to 150
It is.

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

[0028]

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[0029]

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(However, in (1) or (2), R ¹
Represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents 2 to 2 carbon atoms.
A hydrocarbon group of 24, a hydrocarbon amino group of 2 to 24 carbon atoms or a hydrocarbon alkoxy group of 1 to 24 carbon atoms,
³ N represents a polycyclic amino group having 7 or more carbon atoms which forms a skeleton together with a nitrogen atom. )

However, the cis / trans ratio of the saturated polycyclic amino group of the component [C] is 90/10 to 0/100. The upper limit of this ratio is preferably 80/20, particularly preferably 60/40. The lower limit of this ratio is preferably 0/100, particularly preferably 10/90.

As the trans content of the saturated polycyclic amino group increases, the first stage polymerization and the second stage copolymerization activities have the effect of increasing. Further, there is an effect that the ethylene content of the rubber component also increases.

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

R ² has ² to 24 carbon atoms, preferably 2 to 8 carbon atoms.
A hydrocarbon group of 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, or 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms.
To 8 hydrocarbon alkoxy groups. Among them, carbon number 2
To 24 hydrocarbon groups or C2 to C24 hydrocarbon amino groups are preferred.

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

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

R ³ N is a polycyclic amino group having 7 or more, preferably 7 to 40, more preferably 7 to 20 carbon atoms forming a skeleton together with a nitrogen atom. The 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.

When R ³ N is a saturated polycyclic amino group, it has a cis or trans structure.

As specific examples of R ³ NH, as shown by the following chemical structural formula, perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazoline , Perhydroacridine, perhydrophenanthridine, perhydrobenzo
(g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline ,
Amine compounds such as perhydroaceisoquinoline and perhydroiminostilbene, and a part of hydrogen atoms other than nitrogen atoms in the amine compound are alkyl groups,
Examples thereof include amine compounds substituted with a phenyl group or a cycloalkyl group.

[0040]

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Particularly preferred R ³ NH include perhydroquinoline, perhydroisoquinoline and derivatives thereof.

The organosilicon compound represented by the general formula (1) includes a perhydroquinolino compound represented by the general formula (4), a perhydroisoquinolino compound represented by the general formula (5), (Per-hydroquinolino) (per-hydroisoquinolino) compound represented by the formula (5).

[0043]

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[0044]

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[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 number of hydrocarbon substituents on the saturated ring of R ³ N may be one or more.

Examples of the compound represented by the general formula (3) include bis (perhydroquinolino) dimethoxysilane.

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-dimethylper-hydroquinolino) dimethoxysilane,
Bis (3,4-dimethylpa-hydroquinolino) dimethoxysilane, bis (3,5-dimethylpa-hydroquinolino) dimethoxysilane, bis (3,6-dimethylpa-hydroquinolino) dimethoxysilanebis (3,7-dimethylpa-hydroquinolino) dimethoxysilane , Screws (3,
8-dimethylper-hydroquinolino) dimethoxysilane,
Bis (3,9-dimethylper-hydroquinolino) dimethoxysilane, bis (3,10-dimethylper-hydroquinolino) dimethoxysilane, bis (4,5-dimethylper-hydroquinolino) dimethoxysilane, bis (4,6-dimethylper-hydroquinolino) dimethoxy Silane, bis (4,7-dimethylper-hydroquinolino) dimethoxysilane, bis (4,8-dimethylper-hydroquinolino) dimethoxysilane, bis (4.9-dimethylper-hydroquinolino) dimethoxysilane, bis (4,10-dimethylper-hydroquinolino) ) Dimethoxysilane, bis (5,6
-Dimethylper-hydroquinolino) dimethoxysilane, bis (5.7-dimethylper-hydroquinolino) dimethoxysilane, bis (5,8-dimethylper-hydroquinolino)
Dimethoxysilane, bis (5,9-dimethylper-hydroquinolino) dimethoxysilane, bis (5,10-dimethylper-hydroquinolino) dimethoxysilane, bis (6
7-dimethylper-hydroquinolino) dimethoxysilane,
Bis (6,8-dimethylper-hydroquinolino) dimethoxysilane, bis (6,9-dimethylper-hydroquinolino) dimethoxysilane, bis (6,10-dimethylpar-
(Hydroquinolino) dimethoxysilane, bis (7,8-dimethylperhydroquinolino) dimethoxysilane, bis (7,9-dimethylperhydroquinolino) dimethoxysilane, bis (7,10-dimethylperhydroquinolino)
Dimethoxysilane, bis (8,9-dimethylperhydroquinolino) dimethoxysilane, bis (8,10-dimethylperhydroquinolino) dimethoxysilane, bis (9,
Bis (dimethyl-substituted per-hydroquinolino) dimethoxysilane such as 10-dimethylper-hydroquinolino) dimethoxysilane.

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

Further, (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,
Hydroquinolino) (10-methylpa-hydroquinolino)
Examples include compounds such as dimethoxysilane.

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

Examples of the compound represented by the general formula (4) include bis (perhydroisoquinolino) dimethoxysilane.

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-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 (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-methylpa-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) ) (Perhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinolino)
(Perhydroisoquinolino) dimethoxysilane, (9-
Methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane, (10-methyl per-hydroquinolino) (per-hydroisoquinolino) dimethoxysilane,
(2-methylpa-hydroquinolino) (1-methylpa-hydroisoquinolino) dimethoxysilane, (3-methylpa-hydroquinolino) (3-methylpa-hydroisoquinolino) dimethoxysilane, (4-methylpa-hydroquinolino) (4- (5-methylperhydroisoquinolino) dimethoxysilane, (5-methylperhydroisoquinolino) (5-methylperhydroisoquinolino) dimethoxysilane, (6-
Methyl per-hydroquinolino) (6-methyl per-hydroisoquinolino) dimethoxysilane, (7-methyl per-hydroquinolino) (7-methyl per-hydroisoquinolino) dimethoxysilane, (8-methyl per-hydroquinolino)
(8-methylpa-hydroisoquinolino) dimethoxysilane, (9-methylpa-hydroquinolino) (9-methylpa-hydroisoquinolino) dimethoxysilane, (10-methylpa-hydroquinolino) (10-methylpa-hydroisoquinolino) Examples include compounds such as dimethoxysilane.

Further, perhydroindolino compounds, perhydroisoindolino compounds and the like can also be mentioned.

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

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

[0063]

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[0064]

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Examples of the organosilicon compound represented by the general formula (2) include a perhydroquinolino compound represented by the general formula (6) and a perhydrohydroquinolino compound represented by the general formula (7). .

[0066]

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[0067]

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

Examples of the compound represented by the general formula (6) include ethyl (perhydroquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, is
o-propyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, ter-butyl (perhydroquinolino) dimethoxysilane, sec-butyl (perhydroquinolino) dimethoxysilane, n-pentyl (per- (Hydroquinolino) dimethoxysilane, iso-pentyl (perhydroquinolino) dimethoxysilane, cyclopentyl (per-hydroquinolino) dimethoxysilane, n-hexyl (per-hydroquinolino) dimethoxysilane, cyclohexyl (per-hydroquinolino) dimethoxysilane, texyl (per-hydroquinolino) ) Dimethoxysilane, n-octyl (perhydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, piperidino (perhydroquinolino) dimethoxy Silane, diethylamino (Pas -
Perhydroquinolinosilane compounds such as (hydroquinolino) dimethoxysilane.

Ethyl (2-methylperhydroquinolino)
Dimethoxysilane, n-propyl (2-methylper-hydroquinolino) dimethoxysilane, iso-propyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Butyl (2-methylperhydroquinolino) dimethoxysilane, iso-butyl (2-methylperhydroquinolino) dimethoxysilane, ter-butyl (2-methylper
Hydroquinolino) dimethoxysilane, sec-butyl (2
-Methylper-hydroquinolino) dimethoxysilane, n-
Pentyl (2-methylpa-hydroquinolino) dimethoxysilane, iso-pentyl (2-methylpa-hydroquinolino) dimethoxysilane, cyclopentyl (2-methylpa-hydroquinolino) dimethoxysilane, n-hexyl (2-methylpa-hydroquinolino) dimethoxysilane,
Cyclohexyl (2-methylperhydroquinolino) dimethoxysilane, texyl (2-methylperhydroquinolino) dimethoxysilane, n-octyl (2-methylpar-
2- (hydroquinolino) dimethoxysilane and phenyl (2-methylperhydroquinolino) dimethoxysilane
Methyl perhydroquinolinosilane compound is exemplified.

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 (perhydroquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, iso-propyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane , Iso-butyl (perhydroquinolino) dimethoxysilane, ter
-Butyl (perhydroquinolino) dimethoxysilane, se
c-butyl (perhydroquinolino) dimethoxysilane,
Compounds such as n-hexyl (per-hydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, and diethylamino (per-hydroquinolino) dimethoxysilalane are preferred.

The compound represented by the general formula (7) includes ethyl (perhydroisoquinolino) dimethoxysilane, n
-Propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, n-butyl (perhydroisoquinolino)
Dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane, ter-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-pentyl (pa -Hydroisoquinolino) dimethoxysilane,
iso-pentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroisoquinolino)
Dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, texyl (perhydroisoquinolino) dimethoxysilane, n-octyl (perhydroisoquino) Perhydroisoquinolinosilane compounds such as rhino) dimethoxysilane, phenyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane and diethylamino (perhydroisoquinolino) dimethoxysilane Is mentioned.

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-methylperhydroisoquinolino) dimethoxysilane, cyclohexyl (2-methylpara (Hydroisoquinolino) dimethoxysilane, texyl (2-methylperhydroisoquinolino) dimethoxysilane, n-octyl (2-methylperhydroisoquinolino) dimethoxysilane, phenyl (2-methylperhydroisoquinolino) dimethoxy Examples thereof include 2-methyl perhydroisoquinolinosilane compounds such as silane.

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

Among the above compounds, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, iso-propyl (perhydroisoquinolino) dimethoxysilane,
n-butyl (per-hydroisoquinolino) dimethoxysilane, iso-butyl (per-hydroisoquinolino) dimethoxysilane, ter-butyl (per-hydroisoquinolino)
Dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, piperidino (per-hydroisoquinolino) dimethoxysilane, diethylamino (per-hydroisoquino) Compounds such as rhino) dimethoxysilane are preferred.

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

[0077]

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[0078]

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

The above-mentioned organosilicon compound component [C] having specific cis and trans structures can be synthesized using HNR secondary amine having specific cis and trans structures as a raw material. The proportion of cis and trans structures is
It can be determined by gas chromatography and ¹³ C-NMR. 1 and 2 show the cis and trans structures of the secondary amine perhydroisoquinoline (PHIQ) and the organic compound component [C], bis (perhydroisoquinolino) dimethoxysilane (BPIQ), respectively. .

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

In the present invention, a crystalline polymer is produced in the first step by propylene homopolymerization or copolymerization of propylene with another α-olefin in the presence of the above-mentioned catalyst system. Without deactivating the catalyst system, by adding an organosilicon compound [D] in the second step and copolymerizing propylene with an α-olefin other than propylene to produce a rubbery copolymer, Polymers can be produced.

The first stage polymerization may be propylene homopolymerization or copolymerization of propylene with another α-olefin. Butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1 as α-olefin

Hexene-1,4-methylhexene-1,
Octene-1, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene,
Non-cyclic monoolefins such as 9-vinylanthracene. Also, cyclopentene, cyclohexane,
And cyclic monoolefins such as norbornene.
Dicyclopentadiene, 5-ethylidene norbornene-
Examples thereof include diolefins such as 2,4-vinylcyclohexene and 1,5-hexadiene.

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

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

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

The polymerization mode of the present invention includes a slurry polymerization in an inert hydrocarbon solvent, a bulk polymerization in which a monomer in a liquid state is polymerized in a solvent, and a monomer in contact with a catalyst in a gaseous state. Polymerization can be performed by gas phase polymerization or a combination thereof. Among them, it is preferable to carry out the bulk polymerization in which the monomer in the liquid state is polymerized as a solvent in the first step and the gas phase polymerization in which the monomer is brought into contact with the catalyst in the gaseous state in the second step.

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

The gas-phase polymerization is carried out at a temperature and a pressure capable of keeping propylene or a mixed monomer of propylene and another α-olefin in a liquid state. Gas phase polymerization is usually
Atmospheric pressure to 20 kg / cm ² , preferably atmospheric pressure to 10 k
g / cm ² . The polymerization temperature is usually 30 to 95 ° C,
Preferably, it is 40 to 70 ° C. The polymerization time is usually
It is 30 minutes to 10 hours, preferably 1 to 5 hours.

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

For adjusting the molecular weight of the produced polymer, hydrogen may be added to the polymerization system as a chain transfer agent, if necessary. The amount of hydrogen used to produce the α-olefin polymer having the desired stereoregularity, melting point and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions. ~ 3.

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

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

In the present invention, when the above-mentioned pretreated solid or prepolymerized solid is used as a solid catalyst component in the main polymerization, component [C] can be omitted in the main polymerization.

According to the present invention, a propylene block copolymer having a molecular weight distribution (ratio Mw / Mn of weight average molecular weight Mw to number average molecular weight Mn) of 15 or more, more preferably 20 or more, and preferably 50 or less Can be manufactured.

[0097]

Industrial Applicability According to the present invention, a propylene block copolymer having a high stereoregularity and a high melting point, a wide molecular weight distribution, and a high ethylene content of a rubber component in a copolymer is obtained by appropriately controlling the molecular weight with high activity. Can be manufactured while.
The obtained propylene block copolymer has excellent mechanical properties such as rigidity, heat resistance, and tensile strength of the molded article, and has a high die shell value with respect to the shear rate at the time of melting. There is no problem of poor appearance. The propylene block polymer of the present invention is used not only alone, but also as a compounding material, other plastics, blends with elastomers, glass fibers, and inorganic and organic fillers such as talc and the like.
In addition, a crystal nucleating agent can be mixed and used, and although not particularly limited, it can exhibit excellent performance as a structural material for automobiles, home appliances, and the like.

[0098]

Embodiments of the present invention will be described below. Is AS
230 ° C measured according to TM-D1238;
It represents the weight (g) of the molten polymer for 10 minutes under a load of 16 kg.

The isopentad fraction (mmmm)%, which is one of the indices of the stereoregularity of the polymer and whose microtacticity was examined, was found to be equal to Macr in the propylene polymer.
Calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on OMOLECULES 8,687 (1975). ^{The 13} C-NMR spectrum was obtained from JEOL EX
-400 unit, temperature 130, based on TMS
C., measured using o-dichlorobenzene solvent.

The molecular weight distribution was measured using 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 ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn was evaluated.

The measurement of the ethylene content in the resulting copolymer was carried out as follows. The sample is heated and melted on a hot plate of a hot press, cooled under pressure, quenched in a water bath,
Was formed. The film in an infrared spectrophotometer, peak of 974 cm ^-1 and 720 cm ^-1 - measuring the click, on the basis of the previously prepared calibration curve, was calculated ethylene content.

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

[Examples 1 to 3] [Comparative Example 3] (Preparation of catalyst solid component [A]) Anhydrous aluminum chloride 1
5 mmol are added to 40 ml of toluene, then 15 mmol of methyltriethoxysilane are added dropwise with stirring,
After completion of the dropwise addition, the reaction was carried out at 25 ° C. for 1 hour. After cooling the reaction product to −5 ° C., diisopropyl ether 18 containing 30 mmol of butylmagnesium chloride was stirred.
mL was added dropwise to the reaction product in 30 minutes, and the temperature of the reaction solution was kept within a range of -5 to 0C. 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 150 mmol of titanium tetrachloride was added to this suspension,
3.3 mmol of di-n-heptyl phthalate was 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. Furthermore,
The solid was suspended again in 30 mL of toluene, 150 mmol of titanium tetrachloride was added, and the mixture was reacted at 90 ° C. for 1 hour with stirring. At the same temperature, the solid was filtered off, and the solid was washed with toluene and then with n-heptane. The titanium content in the obtained solid catalyst component was 3.55 wt%. This solid was suspended in n-heptane (80 mL) to prepare an n-heptane slurry of a catalyst solid component.

(Preliminary Polymerization) The inside of a 2 L stainless steel autoclave equipped with a stirrer was sufficiently purged with nitrogen, and 1.97 mmol of triethylaluminum (a 2.21 ml solution of n-hexane) was prepared. And bis (perhydroisoquinolino) dimethoxysilane having a trans structure of 0.33 mmol (1.7 ml of n-heptane)
Solution) was injected into the autoclave with a syringe. Next, hydrogen is converted into 4 kg / cm ² at 20 ° C. and liquid propylene 90
0 ml was introduced, the autoclave was immersed in a water bath maintained at 10 ° C., and the inside of the autoclave was stirred by operating a stirrer. Ten minutes later, prepolymerization was started by adding the entire amount of 11.3 mg of the catalyst solid previously set in a Teflon capsule to the system. The prepolymerization was performed at 10 ° C. for 10 minutes.

(Bulk polymerization of propylene homopolymer) After the completion of the prepolymerization, the stirrer was stopped, the autoclave was immediately transferred to a high-temperature bath, and stirring was started to raise the temperature. After reaching 72 ° C., homopolymerization was carried out at the same temperature for 50 minutes. After completion of the homopolymerization, stirring was stopped, unreacted propylene was released, and the inside was sufficiently replaced with nitrogen gas, and then the autoclave was taken out of the bath. The inside of the autoclave was kept at room temperature, and the internal pressure was set to 0.2 kg / cm ² . Set to G,
The weight of the autoclave was measured. The yield of the homopolymer was determined at room temperature before polymerization under an internal pressure of 0.2 kg / cm ² . Calculated from the difference between the weight of the empty autoclave held under the nitrogen atmosphere of G and the weight of the autoclave after homopolymerization. Next, nitrogen pressure was applied to evaluate the basic physical properties of the homopolymer, a part of the homopolymer was withdrawn from the nozzle in the autoclave, and the internal pressure in the autoclave was reduced to 0.2 kg again.
/ Cm ² . By holding the autoclave under a nitrogen atmosphere of G and measuring the weight of the autoclave, the sampling amount was calculated from the weight difference before and after the extraction.

(Ethylene / Propylene Gas Phase Block Copolymerization) The autoclave was transferred to a bath, and stirring was started. At the same temperature, propylene gas was supplied at 200 Ncc / min. , Ethylene gas 100Nc
c / min. To the autoclave, and block copolymerization was started. Copolymerization pressure is 2kg
/ Cm ² . G and a copolymerization reaction was carried out at 70 ° C. for 240 minutes. After completion of the copolymerization reaction, stop stirring,
After discharging the unreacted gas out of the system, the inside of the autoclave was sufficiently purged with nitrogen. Next, the autoclave was taken out of the bath, kept at room temperature, and the internal pressure of the autoclave was set at 0.2 kg / cm ² . After being placed in a nitrogen atmosphere of G, the weight was measured, and the block yield was determined from the difference in weight before and after block copolymerization. The measurement results of the basic physical properties of this block copolymer are shown in Tables 1 to 3.

Comparative Example 1 The inside of a 2 L stainless steel autoclave equipped with a stirrer was sufficiently purged with nitrogen to obtain 1.97 mmol of triethylaluminum (a 2.21 ml solution of n-hexane) and 0.33 of cyclohexylmethyldimethoxysilane. Mmol (a 1.7 ml solution of n-heptane) was injected into the autoclave with a syringe. Next, hydrogen is converted into 4 kg / cm ² at 20 ° C. and liquid propylene 900 m
l, and the same procedure as in Example 1 was carried out to carry out prepolymerization,
Homopolymerization and block copolymerization were performed, and homopolymerization activity and copolymerization activity were calculated. The basic physical properties of the obtained homopolymer and block copolymer were measured, and the results are shown in Tables 1 to 3.

Comparative Example 2 The inside of a 2 L stainless steel autoclave equipped with a stirrer was sufficiently purged with nitrogen, and 1.97 mmol of triethylaluminum (a 2.21 ml solution of n-hexane) and 0.1 ml of triphenylethoxysilane were added.
33 mmol (1.7 ml solution of n-heptane) was injected into the autoclave with a syringe. Next, 4 kg / cm ² of hydrogen at 20 ° C. and 900 ml of liquid propylene were introduced,
Preliminary polymerization, homopolymerization and block copolymerization were carried out in the same manner as in Example 1, and the homopolymerization activity and copolymerization activity were calculated. The basic physical properties of the obtained homopolymer and block copolymer were measured, and the results are shown in Tables 1 to 3.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

[Brief description of the drawings]

FIG. 1 shows the cis and trans structures of the C component of perhydroisoquinoline.

FIG. 2 shows the cis and trans structures of bis (perhydroisoquinolino) dimethoxysilane.

FIG. 3 is a chart showing a preparation method and a polymerization method of the catalyst of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Hashizume 8-1, Goi Minami Coast, Ichihara City, Chiba Prefecture Ube Industries, Ltd. Chiba Petrochemical Plant (72) Inventor Yasuhisa Sakakibara 8 Goi Minami Coast, Ichihara City, Chiba Prefecture No. 1 Ube Industries, Ltd. Polymer Research Laboratory F-term (reference) 4J011 AA05 MA02 MA06 MA11 4J026 HA02 HA04 HA05 HA06 HA13 HA27 HA35 HA48 HA49 HB02 HB03 HB04 HB05 HB06 HB13 HB20 HB35 HB42 HB43 4J028 AA01AABB ACB BC06A BC15B BC16B BC25B BC26B BC34A BC39B CB44A EA02 EB04 EB05 EB09 EB10 EB17 EB18 EB21 EC02 ED01 ED02 ED03 ED05 ED06 ED09 FA01 FA04 GA04 GA06 GA07 GA15 GB01

Claims (2)

[Claims] 1. [A] a solid catalyst component essentially comprising magnesium, titanium, a halogen element and an electron donor, [B]
(A) Propylene or propylene is polymerized with another α-olefin in the presence of a catalyst comprising an organoaluminum compound component and [C] an organosilicon compound component represented by the general formula (1) or (2). To produce a propylene polymer having an α-olefin content of 10% by weight or less,
And (b) a method for producing a propylene block copolymer produced by polymerizing propylene with another α-olefin to produce a propylene polymer having an α-olefin content of 10 to 40% by weight. ] The method for producing a propylene block copolymer, wherein the cis / trans ratio of the polycyclic amino group portion of the organosilicon compound component is 90/10 to 0/100. Embedded image Embedded image (However, in (1) or (2), R ¹ has 1 to ¹ carbon atoms.
8 represents a hydrocarbon group, and R ² represents a hydrocarbon group having ² to 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms or 1 carbon atom.
Shows the 24 hydrocarbon alkoxy group, R ³ N represents a polycyclic amino group having 7 or more carbon atoms in a backbone together with a nitrogen atom. ) 2. Polymerization of propylene or propylene with another α-olefin in the presence of the catalyst comprising [A], [B] and [C] according to claim 1;
A method for producing a propylene block copolymer, comprising performing a gas phase copolymerization of propylene with another α-olefin in the second step without deactivating the above catalyst.