JP2001122917A - METHOD FOR POLYMERIZING alpha-OLEFIN AND alpha-OLEFIN POLYMER PRODUCED BY THE METHOD - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an α-olefin polymer having high activity, high hydrogen responsiveness, high stereoregularity and wide molecular weight distribution. SOLUTION: This method for producing an α-olefin is characterized by polymerizing or copolymerizing an α-olefin in the presence of a catalyst comprising [A] a catalytic solid component indispensably composed of magnesium, titanium, a halogen atom and an electron donor, [B] an organoaluminum compound component and [C] a specific cyclic amino group-containing organosilicon compound component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel catalyst component, which is obtained by performing polymerization using an organosilicon compound having a specific structure, thereby obtaining high activity, high hydrogen sensitivity and high stereoregularity. The present invention also relates to a method for producing a homopolymer of an α-olefin having a wide molecular weight distribution or a copolymer with another α-olefin.

[0002]

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

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

[0004] Also, Japanese Patent Application Laid-Open Nos. 8-1220021, 8-143621 and 8-231636.
In the publication, a method using a cyclic aminosilane compound is disclosed, but the molecular weight distribution is neither described nor suggested. In addition, propylene polymers obtained by polymerization using cyclic aminosilane compounds specifically described in these publications do not always have a wide molecular weight distribution.

Japanese Patent Application Laid-Open Nos. 6-25336, 7-90012, and 7-97411 disclose nitrogen in which an arbitrary carbon atom in a heterocyclic ring is directly bonded to a silicon atom. Although a method using an atom-containing heterocyclic-substituted organosilicon compound is disclosed, there is no description or suggestion about the molecular weight distribution. Also, JP-A-3-74393 and JP-A-7-173212 disclose a method using an organosilicon compound containing a 4- to 8-membered ring monocyclic amino group. There is no description or suggestion.

On the other hand, as a method for producing a propylene polymer having a wide molecular weight distribution and a high stereoregularity, a low stereomolecular propylene polymer having a high stereoregularity previously produced by conventional polymerization is used. A method of melt-mixing a crystalline high molecular weight propylene polymer at a desired ratio can be considered. However, also in this case, it is extremely difficult to uniformly melt-mix the low-molecular-weight propylene polymer and the high-molecular-weight propylene polymer, which causes problems such as gel formation.

Japanese Patent Application Laid-Open No. Hei 10-218926 discloses a method for producing a polymer of an α-olefin having a wide molecular weight distribution by using a specific polycyclic amino group-containing organosilicon compound. In some cases, the polymerization activity is lower than that of the conventional organosilicon compound, and the hydrogen sensitivity is low.

It is also important that the hydrogen sensitivity is high. In other words, in order to adjust the molecular weight of the α-olefin polymer, when hydrogen as a chain transfer agent is allowed to coexist in the polymerization system, if the hydrogen sensitivity is low, a large amount of hydrogen is required. Low-molecular-weight α-olefin polymer must be produced, for example, in a polymerization reactor having a pressure limit, the polymerization temperature must be lowered due to a high hydrogen partial pressure, which adversely affects the production rate. There is a problem.

[0009]

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

[0010]

According to the present invention, there are provided [A] a catalyst solid component essentially containing magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, [C] a general formula (1) Alternatively, the present invention relates to a method for polymerizing an α-olefin, which comprises polymerizing or copolymerizing an α-olefin in the presence of a catalyst comprising an organosilicon compound component represented by (2).

[0011]

Embedded image

[0012]

Embedded image (However, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms;
Is from 8 to 12. )

[0013]

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.
94590, JP-A-5-55405, JP-A-56-45909, JP-A-56-163102
JP, JP-A-57-63310, JP-A-57-63310
115408, JP-A-58-83006,
JP-A-58-83016, JP-A-58-1387
No. 07, JP-A-59-149905, JP-A-60-23404, JP-A-60-32805, JP-A-61-18330, JP-A-61-55
104, JP-A-2-77413, JP-A-2
A method proposed in JP-A-117905 can be employed.

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

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

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

The amount of the compound used in the reaction between the aluminum halide and the silicon compound is determined by the element ratio (Al / Si)
Is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3, and it is preferable to use an inert solvent such as hexane or toluene for the reaction. The reaction temperature is usually 1
The reaction temperature is 0 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is usually 0.2 to 5 hours, preferably 0.5 to 3 hours.

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

The amount of the magnesium compound to be used is usually 0.5 to 3, preferably 1, in terms of an element ratio (Mg / Al) to the aluminum halide used for preparing the reaction product of the aluminum halide and the silicon compound. 5-
The range is 2.3. The reaction temperature is usually -50 to 100
℃, preferably -20 to 50 ℃, the reaction time is usually 0.2
-5 hours, preferably 0.5-3 hours.

The white solid obtained in the reaction of the aluminum halide with the silicon compound and subsequently with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. As a method of contact treatment,
(1) a method in which a solid is treated with a titanium halide compound, then treated with an electron donor, and then treated again with a titanium halide compound; and (2) the solid is treated in the coexistence of a titanium halide compound and an electron donor. After that, a conventionally well-known method such as a method of treating with a titanium halide compound can be employed.

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

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

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

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

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

The organosilicon compound component [C] in the present invention is an organosilicon compound having two monocyclic hydrocarbon amino groups as represented by the general formula (1).

[0028]

Embedded image (However, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and n is 8 to 12.)

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. R ¹ in the general formula (1) may be all the same or different. 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.

The monocyclic hydrocarbon amino group is a 9 to 13-membered monocyclic amino group including a nitrogen atom, and particularly a 9-membered nitrogen-containing nitrogen atom including n = 8. Monocyclic amino groups are preferred.

Specific examples of the organosilicon compound represented by the general formula (1) include bis (azacyclononano) dimethoxysilane, bis (azacyclodecano) dimethoxysilane, bis (azacycloundecano) dimethoxysilane,
Bis (azacyclododecano) dimethoxysilane, bis (azacyclotridecano) dimethoxysilane, bis (azacyclononano) diethoxysilane, bis (azacyclodecano) diethoxysilane, bis (azacycloundecano) diethoxysilane, bis (aza) Cyclododecano) dimethoxysilane and bis (azacyclotridecano) diethoxysilane, especially bis (azacyclononano)
Dimethoxysilane is preferred.

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

Embedded image

The organosilicon compound component [C] in the present invention is an organosilicon compound having one monocyclic hydrocarbon amino group as represented by the general formula (2).

Embedded image (However, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and n is 8 to 12.)

The organosilicon compound component [C] in the present invention is an organosilicon compound having one monocyclic hydrocarbon amino group as represented by the general formula (2).

Specific examples of the organosilicon compound represented by the general formula (2) include ethyl (azacyclononano) dimethoxysilane, ethyl (azacyclodecano) dimethoxysilane, bis (azacycloundecano) dimethoxysilane, and ethyl (azacyclododecano). ) Dimethoxysilane,
Ethyl (azacyclotridecano) dimethoxysilane, ethyl (azacyclononano) diethoxysilane, ethyl (azacyclodecano) diethoxysilane, bis (azacycloundecano) diethoxysilane, ethyl (azacyclododecano) diethoxysilane, ethyl ( (Azacyclotridecano) diethoxysilane; and ethyl (azacyclononano) dimethoxysilane is particularly preferable.

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

[0037]

Embedded image

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

The organosilicon compound component [C] represented by the general formula (2) can be easily synthesized by, for example, an equivalent reaction of ethyltrimethoxysilane with a magnesium salt or a lithium salt of a hydrocarbon amine.

In the present invention, in addition to the above [A] and [B], [C] the above general formula (1) or (2)
Α-olefin is polymerized or copolymerized with a catalyst comprising an organosilicon compound component represented by the formula:

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

The polymerization pressure is 0.1 to 20 MPa, preferably 1 to 6 MPa, and the polymerization temperature is 10 to 150 ° C., preferably 30 to 100 ° C., particularly preferably 60 to 90 ° C. The polymerization time is generally 0.1 to 10 hours, preferably 0.1 to 10 hours.
The range is 5 to 7 hours.

In the present invention, ethylene or α-
It is preferable that the olefin is preliminarily polymerized according to the above-mentioned various polymerization methods, and then the main polymerization of the α-olefin is performed.
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. Catalyst solid component [A], organoaluminum compound component [B] and organosilicon compound component [C]
With a limited amount of ethylene or α-
A prepolymerized solid can be prepared by polymerizing an olefin. In some cases, it is possible to prepare a pre-treated solid obtained by contact-treating the catalyst solid component [A] with the organoaluminum component [B] and the organosilicon compound component [C] without polymerizing ethylene or α-olefin. it can.

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

The contact treatment of the present invention includes components [A],
The component [B] and the component [C] are mixed, and usually 0 to 100
React at 0.1 ° C for 0.1 to 10 hours. The mixing order of each component is
Although not particularly limited, usually, component [A], component [B],
The order of component [C] is preferred. After the contact treatment, the solid is washed with an inert hydrocarbon solvent such as n-heptane, filtered,
Separated and used as a catalyst solid component for prepolymerization or main polymerization.

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.

The prepolymerization time is usually 0.1 to 10 hours, and it is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the solid catalyst component. If the amount is less than 0.1 g per 1 g of the solid catalyst component, the main polymerization activity is not sufficient and the amount of catalyst residues increases, and the stereoregularity of the α-olefin polymer is not sufficient. Also, 100
If it exceeds g, the polymerization activity and the crystallinity of the α-olefin polymer tend to decrease. The prepolymerization temperature is from 0 to 1
The reaction is carried out at 00 ° C, preferably 10 to 70 ° C, in the presence of each catalyst component. When prepolymerization is carried out at a temperature higher than 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 may be reduced in the main polymerization or the crystallinity of the obtained α-olefin polymer may be reduced. Or decrease.

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

In the present invention, when the organoaluminum compound component [B] is used at the time of the main polymerization, the amount of the component [B] used is A with respect to the titanium atom of the solid catalyst component [A].
l / Ti molar ratio is 10 to 800, preferably 10 to 60
0.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used to produce the α-olefin polymer having the desired stereoregularity, melting point and molecular weight can be appropriately determined depending on the polymerization method and the polymerization conditions. ~ 3
Range.

In the method for polymerizing an α-olefin according to the present invention, the polymerization activity is further increased by adding an organosilicon compound component [C] in addition to the organoaluminum compound component [B] during the main polymerization of the α-olefin. And the stereoregularity of the polymer can be improved.

In the present invention, examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methylpentene-1, 3-methylbutene-1, and 1-octene. In the present invention, the film
In order to lower the sealing temperature, the α-olefin may be copolymerized with a small amount of ethylene or another α-olefin in the polymerization of α-olefin for the purpose of lowering the melting point or increasing the transparency of the film.

In order to increase the low-temperature impact strength of a molded article of an α-olefin polymer, a so-called block copolymer is obtained by further copolymerizing the α-olefin and ethylene after the above-mentioned polymerization and copolymerization of the α-olefin. Can also be manufactured.

The catalyst system of the present invention has high catalytic activity,
Moreover, the obtained α-olefin polymer has high stereoregularity and wide molecular weight distribution. The molecular weight distribution was determined by weight average molecular weight M obtained by GPC measurement in terms of polystyrene.
w and the number average molecular weight Mn (Mw / Mn value) is 10
20, more preferably 12 to 18.

The α-olefin polymer obtained by the present invention has a high melt viscoelasticity due to its wide molecular weight distribution, and is particularly excellent in film formability and drawdown property of a film and the like, as well as rigidity and heat resistance of an injection molded article. It is excellent in mechanical properties such as properties and tensile strength, and there is no problem of poor appearance of a molded product represented by a flow mark. The α-olefin polymer obtained in the present invention is used not only alone, but also as a compounding material, other plastics, blends with elastomers, glass fibers, and inorganic or organic fillers such as talc, reinforcing agents for organic fillers, 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.

[0056]

When the α-olefin is polymerized by the catalyst of the present invention, in particular, a catalyst using a monocyclic amino-containing organosilicon compound having a specified number of ring-forming members as an external electron donor, the polymerization activity is increased. Α-olefin polymer having a high molecular weight distribution, a high hydrogen sensitivity, a high stereoregularity, and a wide molecular weight distribution can be produced. Furthermore, in the copolymerization with ethylene or another α-olefin, a copolymer having good randomness and high melt viscoelasticity can be produced.

The α-olefin polymer obtained in the present invention has the same molecular weight distribution as the α-olefin polymer obtained with a conventional titanium trichloride type catalyst having a low polymerization activity and called a second generation catalyst. Therefore, the moldability is good and there is no problem such as poor appearance of a molded article such as a flow mark. Therefore, the catalyst system used in the present invention can be used as a substitute for the titanium trichloride type catalyst, and has a very high polymerization activity as compared with the titanium trichloride type catalyst. Step of removing the catalyst residue of, that is, the deashing step using a large amount of organic solvent can be omitted,
This is useful for simplifying the polymerization process and reducing the production cost.

[0058]

Embodiments of the present invention will be described below. In the examples, “polymerization activity” refers to α-
It is the yield (Kg) of the olefin polymer.

The melt flowability (MFR) was measured according to ASTM-D1.
Represents the weight (g) of the molten polymer at 230 ° C. under a load of 2.16 Kg for 10 minutes measured according to 238.

The melting point (Tm) was measured using DSC (SSC-5200 DSC-220C manufactured by Seiko Instruments Inc.). Measurement method is 10 ° C / min from room temperature to 230 ° C.
The temperature was raised at a speed of
After the temperature was decreased from 5 ° C. to 40 ° C. at a rate of 5 ° C./min, the temperature was further increased from 40 ° C. to 230 ° C. at a rate of 10 ° C./min, and the melting point was measured.

The isopentad fraction (mmm) was determined by examining the microtacticity, which is an index of the tacticity of the polymer.
m)% is Macromol in propylene polymer
calculated from the peak intensity ratio of the ¹³ C-NMR spectrum assigned based on Eucules 8,687 (1975). ^{The 13} C-NMR spectrum is EX-4 manufactured by JEOL Ltd.
The temperature of 130 ° C., based on TMS,
The measurement was performed using an o-dichlorobenzene solvent.

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

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

(3) Polymerization of Propylene In a 2-liter stainless steel autoclave equipped with a stirrer, 2.1 mmol of triethylaluminum is used as the organic aluminum compound component [B], and bis (azacyclononano) dimethoxy is used as the component [C]. 0.36 mm silane
After injection, 0.005 mmol of n-heptane slurry of the catalyst solid component obtained above in terms of titanium atoms was injected using a gas tight syringe, and then 0.12 M
Hydrogen of Pa and 1.2 L of liquefied propylene were introduced. Oh
The reactor was cooled to 10 ° C. in a cooling bath, stirring was started, and prepolymerization was performed for 10 minutes. Subsequently, the autoclave was transferred to a cooling bath, the temperature was raised to 70 ° C, and polymerization was performed at 70 ° C for 1 hour. After completion of the polymerization, unreacted propylene gas was released, and the polymer was dried under reduced pressure at 50 ° C. for 20 hours to obtain a white powdery polypropylene. The results are shown in Tables 1 and 2.

Example 2 Example 2 was repeated except that bis (azacyclotridecano) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane. The results are shown in Tables 1 and 2.

Example 3 The procedure of Example 1 was repeated except that ethyl (azacyclononano) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane. The results are shown in Tables 1 and 2.

Example 4 The procedure of Example 1 was repeated except that ethyl (azacyclotridecano) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane. The results are shown in Tables 1 and 2.

Comparative Example 1 The procedure of Example 1 was repeated, except that cyclohexyl (methyl) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane as the component [C]. The results are shown in Tables 1 and 2.

Comparative Example 2 The same operation as in Example 1 was carried out except that di (hexamethyleneimino) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane as component [C]. The results are shown in Tables 1 and 2.

Comparative Example 3 The same procedure as in Example 1 was carried out except that bis (perhydroisoquinolino) dimethoxysilane was used instead of bis (azacyclononano) dimethoxysilane as component [C]. The results are shown in Tables 1 and 2.

[0071]

[Table 1]

[0072]

[Table 2]

[Brief description of the drawings]

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

Continued on the front page F term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A BA02A BA02B BB00A BB01B BC06A BC15B BC34A BC34B CA18A CA19A CB44A CB92A EB02 EB03 EB04 EB05 EB07 EB09 EB10 EC01 EC02

Claims (3)

[Claims] [1] A catalyst solid component essentially comprising [A] magnesium, titanium, a halogen element and an electron donor, [B] an organoaluminum compound component, and [C] a compound represented by the general formula (1) or (2). Organosilicon compound component to be used Embedded image (Wherein R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and n is 8 to 12). Α-olefin is polymerized or copolymerized in the presence of a catalyst comprising α-olefin. Olefin polymerization method. 2. The ratio (Mw / Mn value) between the weight average molecular weight Mw and the number average molecular weight Mn of the α-olefin polymer produced by the polymerization method according to claim 1 in terms of polystyrene by GPC measurement. Is from 10 to 20. The method for polymerizing α-olefins according to claim 1, wherein 3. An α-olefin polymer produced by the method for polymerizing an α-olefin according to claim 1.