JP2778130B2 - Method for producing olefin polymer - Google Patents

Description

The present invention relates to a method for producing an olefin polymer using a novel solid catalyst component. More specifically, a novel catalyst component with a carrier that provides a polymer having excellent polymerization activity, stereoregularity, and particle properties, an organometallic compound of a metal in Groups I to III of the Periodic Table, and electron donation as needed. The present invention relates to a method for producing an α-olefin polymer such as propylene, butene-1, 4-methylpentene-1, and 3-methylbutene-1 using a catalyst composed of an acidic compound.

In particular, the present invention relates to a method for producing a polymer having high activity, high stereoregularity and good particle properties for α-olefins having 3 or more carbon atoms.

[Conventional technology]

Heretofore, there have been many proposals for a method for producing a catalyst that gives a highly active and highly stereoregular polymer to an α-olefin having 3 or more carbon atoms using a supported catalyst. Many proposals have also been made on a method for producing a catalyst component in which the obtained polymer has improved particle properties. However, many of them do not sufficiently satisfy all of the polymerization activity, stereoregularity and particle properties, and further improvement is desired.

The present inventors have previously described a process for producing a catalyst component excellent in polymerization activity, stereoregularity and particle properties, as disclosed in JP-A-63-10 / 1988.
No. 8008, a method in which a magnesium alkoxide is heated and reacted with a silicon tetraalkoxide and then treated with an electron-donating compound and a halogen-containing titanium compound, and in JP-A-64-54007, a method of converting a magnesium alkoxide into a titanium tetraalkoxide and a silicon tetraalkoxide And a treatment with an electron-donating compound and a halogen-containing titanium compound after heat-reacting the compound, but further improvement in polymerization activity has been desired.

[Means for solving the problem]

The present inventors have intensively studied a method for producing a solid catalyst component having a higher polymerization activity while maintaining high tacticity and good particle properties of the above-mentioned catalyst system, and have reached the present invention. . That is, the gist of the present invention consists of at least magnesium, silicon and one or two or more OR ¹ groups (wherein R ¹ represents an alkyl group, an aryl group or an aralkyl group), and contains titanium if necessary. halogen-containing titanium compound component (a) to (b), the general formula SiX _n R ³ _4-n (wherein R ³ represents an alkyl group, an aryl group or an aralkyl group, X is a halogen atom,
n represents 4 ≧ n> 0. ), And a solid catalyst component (A) obtained by contacting with a halogen-containing silicon compound (c) and an electron donating compound (d), and an organometallic compound (B) of a metal belonging to Group I to III of the periodic table. And, if necessary, a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an electron-donating compound (C).

The present invention will be described in detail. (A) A component comprising at least magnesium, silicon and one or two or more OR ¹ groups and optionally containing titanium, (b) a halogen-containing titanium compound, and (c) a general formula SiX _n R ³ a halogen-containing silicon compound represented by the _4-n, and (d) is obtained by contact treatment with an electron-donating compound as a solid catalyst component (A)
And an organometallic compound (B) of a metal belonging to Group I to III of the periodic table as an essential component, and an olefin is polymerized or copolymerized using a catalyst in which an electron-donating compound (C) is appropriately combined. Is a method for producing an olefin polymer.

The method for obtaining the component (a) is not particularly limited, but a preferred method is to use the general formula Mg (OR ⁴ ) _n (OR ⁵ ) _2-n (wherein R ⁴
And R ⁵ represent an alkyl group, an aryl group or an aralkyl group, and R ⁴ and R ⁵ may be the same or different. n is 2 ≧ n
Indicates the number of ≧ 0. Magnesium compounds represented by) (a _1), the general formula Si _(OR ⁶⁾ 4 (wherein R ⁶ is an alkyl group, an aryl group or an aralkyl group.) A silicon compound represented by (a _2), and needs Depending on the general formula Ti (O
R ⁷⁾ 4 _(wherein R ⁷ is an alkyl group, an aryl group or an aralkyl group.) Titanium represented by compound (a ₃₎ and / or R ⁸ OH (wherein R ⁸ is an alkyl group, an aryl group, or Which represents an aralkyl group).

Hereinafter, a method for obtaining the above component (a) will be described in detail. Specific examples of the magnesium compound (a ₁ ) represented by the general formula Mg (OR ⁴ ) _n (OR ⁵ ) _2-n include Mg (OCH ₃ ) ₂ ,
Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₃ H ₇ ) ₂ , Mg (OC ₄ H ₉ ) ₂ , Mg (O
_{C 6 H 5) 2, Mg} (OCH 2 C 6 H 5) 2, Mg (OC 2 H 5) (OC 4 H 9),
Mg (OC ₆ H ₅ ) (OC ₄ H ₉ ), Mg (OC ₂ H ₅ ) (OC ₆ H ₅ ), Mg (OC
Dialkoxy magnesium such as ₆ H ₄ CH _{3) 2,} diaryloxy magnesium, may be mentioned di aralkyloxy magnesium, alkyloxy aryloxy magnesium. These can be used as a mixture.

Examples of the silicon compound (a ₂ ) represented by the general formula Si (OR ⁶ ) ₄ include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
Examples thereof include tetra (2-ethylhexoxy) silane, tetraphenoxysilane, and tetra (p-methylphenoxy) silane. These can be used as a mixture.

Examples of the titanium compound (a ₃ ) represented by the general formula Ti (OR ⁷ ) ₄ include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , and Ti (OC
_{3 H 7) 4, Ti (} OC 4 H 9) 4, Ti (OC 6 H 5) 4, Ti (OCH 2 C 6 H
₅ ) _{4 and the} like. These can be used as a mixture.

As the compound (a ₄ ) represented by the general formula R ⁸ OH, ethanol, isopropanol, propanol, butanol,
Alcohols such as isobutanol, hexanol, octanol, 2-ethylhexanol and benzyl alcohol; and phenols such as phenol, cresol, xylenol and butylphenol.

Among these, magnesium compounds, silicon compounds,
It is preferable that either the titanium compound or the compound represented by R ⁸ OH contains an aryloxy group as an OR group (R represents an alkyl group, an aryl group or an aralkyl group).

Magnesium compound (a ₁ ) and silicon compound (a ₂ ) and, if necessary, titanium compound (a ₃ ) and / or R ⁸ OH
As a method for obtaining a component (a) by reacting two to four compounds of the compound (a ₄ ) represented by (a), (a ₁ ), (a ₂ ), and if necessary, (a ₃ ) and / or ( a method of reacting by contacting a ₄₎ simultaneously, (a _1), a method of reacting (a ₂₎ or _{(a 1), (a 2} ), after reaction _{(a 3) (a 4)} , A method of reacting (a ₁ ) with (a ₂ ) followed by reacting (a ₃ ) and, if necessary, (a ₄ ), (a ₁ )
After reacting (a ₂ ) or (a ₁ ), (a ₂ ) and (a ₄ ),
A method of reacting (a ₃ ) or a method of reacting (a ₁ ), (a ₄ ) or (a ₁ ), (a ₃ ), (a ₄ ) and then reacting (a ₂ ), etc. Can be During the reaction, an inert hydrocarbon solvent such as hexane, heptane, pentane, butane, toluene and xylene may be present. Reaction temperature is 60 ° C
To 200 ° C., preferably 100 ° C. to 150 ° C., and the reaction time is about 0.5 to 4 hours. The amounts used of the respective components are generally as follows when expressed in a molar ratio.

_{^{Mg (OR 1) n (OR}} 2) Si (OR 3) with respect to _2-n 1 _{4 0.1~5,} preferably _{^{0.2~2 Ti (OR 4) 4 0~4}} , preferably 0.2 to 1 R ⁵ OH 0 to 5, preferably 1 to 3 It is particularly preferred to use the above-mentioned heated reaction products as component (a) in the present invention. Also, in the above reaction,
It is possible to obtain a liquid material by the composition ratio of (a ₁ ), (a ₂ ) and, if necessary, (a ₃ ) and / or (a ₄ ). Good results are often obtained when a slurry containing the substance is used as the component (a).

In the present invention, the component (a) obtained as described above is used in the presence or absence of an inert hydrocarbon solvent such as hexane, heptane, pentane, butane, and toluene to form a halogen-containing titanium compound (b), The solid catalyst component (A) is obtained by performing a contact treatment with the containing silicon compound (c) and the electron donating compound (d).

Examples of the halogen-containing titanium compound (b) used here include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and a titanium halogen / alcoholate compound. Of these, titanium tetrachloride and titanium halogen
An alcoholate compound is used.

The general formula SiX _n R ³ _4-n (wherein R ³ represents an alkyl group, an aryl group or an aralkyl group, X is a halogen atom, n represents 4
≧ n> 0. )) Include SiCl ₄ , SiBr ₄ , SiI ₄ , SiCl (C
H ₃ ) ₃ , SiCl ₂ (CH ₃ ) ₂ , SiCl ₃ (CH ₃ ), SiCl (C ₂ H ₅ )
₃ , SiCl ₂ (C ₂ H ₅ ) ₂ , SiCl ₃ (C ₂ H ₅ ), SiCl (C
_{3 H 7) 3, SiCl 2} (C 3 H 7) 2, SiCl 3 (C 3 H 7), SiCl (C 6 H
₅ ) ₃ , SiCl ₂ (C ₆ H ₅ ) ₂ , SiCl ₃ (C ₆ H ₅ ) and the like.

The electron donating compound (d) generally includes a phosphorus-containing compound, an oxygen-containing compound, a sulfur-containing compound, and a nitrogen-containing compound. Of these, an oxygen-containing compound is preferably used.

As the oxygen compound, for example, the following general formula (Wherein, R ⁹ and R ¹⁰ represent a hydrocarbon group which may be substituted with an alkoxy group, and may be mutually bonded to form a cyclic group. K represents a number of 1 to 3) )). Specifically, diethyl ether,
Ethers such as dipropyl ether, diethylene glycol, polypropylene glycol, ethylene oxide, propylene oxide, and furan; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and phenyl propyl ketone; ethyl acetate, methyl propionate, and acrylic acid Ethyl, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, methyl ethyl benzoate , Ethyl ethyl benzoate, ethyl xylene carboxylate, methyl anisate, ethyl anisate, methyl ethoxy benzoate, ethyl ethoxy benzoate, ethyl cinnamate, di phthalate Chill, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, esters of such carboxylic acid dioctyl _{phthalate, o-C 6 H 4 (} CO
_{O) 2 Mg, o-C} 6 H 4 (COO) 2 AlCl, (o-C 6 H 4) 3 (COO) 6
Carboxylic acid derivatives such as B ₂ (C ₆ H ₅ COO) ₂ AlOH or γ
Cyclic esters such as -butyl lactone; and silicon-containing carboxylic esters such as -β-trimethoxysilylethyl benzoate and bistrimethylsilyl phthalate. Preferably carboxylic esters,
Carboxylic acid derivatives are used.

In the method of the present invention, (a), (b), (c),
As the contact treatment method of the component (d), (1) a method of treating (a) with (b) + (c) + (d) (2) a contact between (a) and (b) + (c) in advance (3) A method in which (a) and (b) are brought into contact in advance and then a method in which treatment is carried out in (c) and (d) (4) (a) and (d) are brought into contact in advance (5) Method in which (a) and (c) are brought into contact in advance and then processed in (b) and (d) (6) Reactant (a) (D) co-existing and reacting, and then treating with (b) and (c) (7) treating (a) and (b) in advance, contacting with (c), (8) A method in which (a) is processed in (b), (c) and (d), in which each component is divided and processed. For example, a method in which (a) and (b) are brought into contact in advance, then treated in (b) and (c), and then treated in (d). (9) There is a method of repeating the processing step of (b), (c) and / or (d) at least twice or more in the step of processing d). Of the above methods, usually, (2) and (3) , (7),
The methods (8) and (9) are adopted.

After the treatment, the solid catalyst component (A) is obtained by washing with an inert hydrocarbon solution to remove components soluble in the solvent.

The amount of each of the components (b), (c) and (d) used in the catalyst production step in one step is usually expressed as a molar ratio with respect to 1 mol of the magnesium compound in the component (a). It is.

Halogen-containing titanium compound (b) 0.1 to 100, preferably 1 to 40 halogen-containing silicon compound (c) 0.01 to 10, preferably 0.1 to 5 electron-donating compound (d) 0.01 to 10, preferably 0.05 to 1; The amount of each of the above components is adjusted so that the titanium content in the obtained solid catalyst component (A) is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

The contact treatment temperature is usually −70 ° C. to 200 ° C., preferably −30 ° C.
C. to 150C. Specifically, taking the contact treatment method shown in (3) above as an example, the component (a) and the component (b) are contacted at -70 ° C to 50 ° C, preferably -30 ° C to 30 ° C, Good results can be obtained by treating the components (c) and (d) by contacting them at 50 ° C to 200 ° C, preferably 50 ° C to 150 ° C.

When the contact temperature is lowered as described above, the components (a) and (b) and optionally the component (c) and / or
Alternatively, when the component (d) is brought into contact, the whole is likely to become a uniform liquid once, and the solid liquid is heated and heated to precipitate a solid, whereby a solid catalyst component having good particle properties can be obtained.

The treatment can be performed in the presence or absence of an inert solvent, and the treatment time is about 0.5 to 6 hours.

The solid contact component (A) thus obtained and the periodic table I to
A polyolefin is produced by polymerizing or copolymerizing an olefin using a catalyst system comprising a mixture of an organometallic compound of a Group III metal (B) and, if necessary, an electron-donating compound (C).

As the organometallic compound (B) of a metal belonging to Groups I to III of the periodic table used in this catalyst system, preferably, a compound represented by the general formula Al
And a compound represented by R ¹¹ _m X _3-m . In the above formula, R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, particularly an aliphatic hydrocarbon group, X is a halogen, and m is a number of 2 to 3.
Specific examples of the organoaluminum compound include triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethylaluminum monochloride, and the like. Can be

As the electron-donating compound (C), the component (d) used in the production of the solid catalyst component (A) is used, and is preferably a carboxylate, and particularly preferably an aromatic carboxylate. Further, silicon-containing compounds such as tetraethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane, and piperidine derivatives such as 2,2,6,6-tetramethylpiperidine are also preferably used.

The molar ratio of the titanium component in the catalyst component (A) to the aluminum compound of the component (B) to the electron donating compound of the component (C) in the catalyst component (A) is preferably 1: 3 to 500: 10 to 100. 1: 20 ~ 200: 3 ~ 50.

Examples of the olefin to be subjected to polymerization or copolymerization include propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1 and the like, preferably α-olefins having 3 or more carbon atoms, particularly propylene. Can be The polymerization can be suitably applied to random or block copolymerization in addition to homopolymerization.

The polymerization reaction is carried out using a slurry polymerization method using an inert hydrocarbon such as hexane, heptane, toluene, pentane, butane or a mixture thereof, or a liquefied α-olefin to be polymerized as a solvent, or a gas that allows polymerization in a gas phase. It can be carried out by a phase polymerization method.

The temperature is 50 to 100 ° C., preferably 60 to 90 ° C., and the pressure is not particularly limited, but is usually selected from the range of atmospheric pressure to 100 atm.

Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

Other means usually employed for the polymerization and copolymerization of each α-olefin can also be applied to the method of the present invention. For example, the α-olefin is prepolymerized by using the three components of the catalyst (A), (B), (C) or the two components (A) and (B), and then the α-olefin is heated at a temperature higher than the prepolymerization temperature. This is a method of polymerizing. At this time, the pre-polymerization amount is selected from about 0.1 to 100 g per 1 g of the catalyst component (A).
Generally, about 1 to 3 g is sufficient. After the obtained prepolymerization catalyst component is washed with an inert hydrocarbon such as hexane, it may be used in the main polymerization or may be used without washing.

〔Example〕

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples at all without departing from the gist thereof.

FIG. 1 is a flowchart for helping to understand the technical contents included in the present invention, and the present invention is not limited by the flowchart unless it departs from the gist.

In Examples, the polymerization activity (shown as K) is the amount of polymer produced (g) per 1 g of the solid catalyst component (A) per α-olefin pressure of 1 kg / cm ² per hour, and the catalyst efficiency (CE). Is the amount (g) of polymer produced per gram of the solid catalyst component (A).

The isotactic index (indicated as II) is the remaining (wt%) when extracted with boiling n-heptane for 6 hours with a modified Soxhlet extractor.

Bulk density (shown as ρB; unit is g / cc) is JIS-K-6
Measured according to 721. Melt flow index (MFI
) Were measured according to ASTM-D-1238.

The particle size distribution of the polymer was measured using a standard sieve of Mitamura Riken Co., Ltd.

Example 1 (1) Production of Catalyst Component (A) After sufficiently replacing a 500 ml flask equipped with a stirrer and a thermometer with purified N ₂ , 5 g of commercial Mg (OC ₂ H ₅ ) ₂ was added under a purified N ₂ seal.
g, and a toluene solution of Ti (OC ₄ H ₉ ) ₄ 7.4 g and tetraphenoxy silane 8.8 g was added.
The reaction was carried out at 0 ° C. for 2 hours to obtain a reaction product (a) as a yellow slurry.

After the reaction, 87 ml of purified toluene was added, and the mixture was cooled to −20 ° C., and at −20 ° C., 24.8 gr of TiCl ₄ was added. After the addition, the whole became a homogeneous solution. When the temperature was gradually increased after the addition, precipitation of particles was observed during the temperature increase. After the temperature was raised to 110 ° C., 9.2 gr of SiCl ₃ (C ₆ H ₅ ) and 1.3 gr of ethyl benzoate were added, and the mixture was kept at the same temperature for 1 hour. Thereafter, the solid was washed with purified toluene to obtain a solid product.

Next, 41 gr of TiCl ₄ and 1.3 gr of ethyl benzoate were added, and the solid product was treated at 80 ° C. for 1 hour, and then sufficiently washed with purified toluene to obtain 5.0 gr of a solid catalyst component. The amount of supported Ti was 3.0% by weight.

(2) the second induction stirring type autoclave was sufficiently replaced with polymerization purified argon propylene, under argon seal, added triethylaluminum 1.0 mmol, a para-methyl methyl 0.3mmol benzoate at room temperature, further 1.0kg of H ₂ at room temperature / cm ² and 700 g of liquid propylene was charged. Next, after adding 9 mg of the solid catalyst, the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. Thereafter, excess propylene was purged to obtain 450 gr of powdered polypropylene. Catalyst efficiency CE is 50,000g-pp
/ gr-cat, polymerization activity K was 1670. ρB is 0.44g / cc
The II was 96.5% and the MFI was 4.9. The particle size distribution of the obtained polymer is very narrow, and the powder having a particle diameter of 400 μm to 200 μm is 96% of the whole, and the amount of fine powder of 100 μm or less is 0.2%.
Met.

Example 2 (1) commercially available Mg (OC ₂ H ₅₎ in Production Example 1 (1) and the same method of the catalyst component (A) ₂ 5Gr
And 8.8 gr of a toluene solution of tetraphenoxysilane, and then the mixture was heated and reacted at 130 ° C. for 2 hours.

The reaction product was a white solid slurry. After the reaction, 67 ml of purified toluene was added, and the mixture was cooled to -20 ° C. -20 ° C
In 17g of TiCl ₄ was added. After the addition, gradually raise the temperature to 8
After heating to 0 ° C, 18.5 gr of SiCl ₃ (C ₆ H ₅ ) and ethyl benzoate
1.3 gr was added. After the addition, the temperature was further raised to 110 ° C. and maintained at the same temperature for 1 hour. Thereafter, the solid was washed with purified toluene to obtain a solid product.

Next, TiCl ₄ 829r and 1.3 gr of ethyl benzoate were added, and 80
After treating the solid product at 1 ° C. for 1 hour, the solid product was washed with purified toluene to obtain 5.0 gr of a solid catalyst component. Ti of this thing
The carried amount was 2.7% by weight.

(2) Polymerization of propylene When propylene was polymerized in the same manner as in Example 1 (2), the catalyst efficiency CE was 34,500 g-pp / g-Cat polymerization activity K.
Was 1150. ρ _B is 0.42 g / cc, II is 96.9%, MFI is
It was 5.6. When the particle size distribution of the obtained polymer was measured, the powder having a particle size of 400 μm to 150 μm was found to be 92% in total.
%, The differential amount below 100 μm was 0.3%, and the particle size distribution was narrow.

Example 3 (1) commercially available Mg (OC ₂ H ₅₎ in Production Example 1 (1) and the same method of the catalyst component (A) ₂ 5 g
r, Ti (OC ₄ H ₉ ) ₄ 7.4 gr and tetraethoxysilane 4.6 g
and the mixture was heated under stirring. Phenol after heating to 130 ° C
8.2 gr of toluene solution was added. After the addition, the mixture was reacted at 130 ° C. for 1 hour to obtain a reaction product in the form of a yellow solid slurry.

After the reaction, 87 ml of purified toluene was added, and the mixture was cooled to −20 ° C., and at −20 ° C., 24.8 gr of TiCl ₄ was added. After the addition, the temperature was gradually raised, and at 50 ° C., 18.5 gr of SiCl ₃ (C ₆ H ₅ ) was added. Thereafter, the temperature was further raised, and 1.3 g of ethyl benzoate was added at 110 ° C., and the mixture was kept at the same temperature for 1 hour. Thereafter, the solid was washed with purified toluene to obtain a solid product. Then TiCl ₄ 4
After adding 1 gr and 1.3 gr of ethyl benzoate, treating the solid product at 80 ° C. for 1 hour, washing with purified toluene,
4.6 gr of a solid catalyst component was obtained. The amount of supported Ti was 2.9% by weight.

(2) Polymerization of propylene When propylene was polymerized in the same manner as in Example 1 (2), the catalyst efficiency CE was 46,500 g-pp / g-cat, and the polymerization activity K was 1550. ρ _B is 0.43 g / cc, II is 97.2%, MFI
Was 4.2. The particle size distribution of the obtained polymer is 400 μm
The powder having a particle size of ~ 150 μm accounts for 96% of the total,
The amount of fine powder having a size of 00 μm or less was 0.2%.

Example 4 In Example 3 (1), SiCl ₄ was used instead of SiCl ₃ (C ₆ H ₅ ).
A solid catalyst component was obtained in the same manner as in Example 3 (1) except that 14.8 gr was used. When propylene was polymerized using this solid catalyst component in the same manner as in Example 1 (2), the catalyst efficiency CE was 40,000 g-pp / g-cat, and the polymerization activity K was
1330. ρ _B is 0.42 g / cc, II is 97.5%, MFI is 3,8
Met.

Example 5 In Example 3 (1), SiCl ₃ (C ₆ H ₅ ) was used instead of SiCl _3.
A solid catalyst component was obtained in the same manner as in Example 3 (1) except that 13.0 gr of (CH ₃ ) was used. This was used in Example 1 (2).
When propylene was polymerized in the same manner as described above, the catalyst efficiency CE was 43,500 g-pp / g-cat, and the polymerization activity K was 1450.
Met. ρ _B is 0.41 g / cc, II is 97.3%, MFI is
It was 5.6.

Example 6 (1) Production Commercial Mg (OC ₂ H ₅₎ of the catalyst component _{(A) 2 5gr, Ti (} OC 4 H 9) 4 6.7gr, using a toluene solution of tetraethoxysilane 4.6gr and phenol 8.2g A reaction product was obtained in the same manner as in Example 3 (1).

Then, after adding 87 ml of purified toluene to this,-
After cooling to 20 ° C., at −20 ° C., 24.8 gr of TiCl ₄ were added. After the addition, the temperature is gradually increased, and at 50 ° C., SiCl ₃ (C ₆ H ₅ ) 2
7.7 gr and 24.8 gr of TiCl ₄ were added. Thereafter, the temperature was further increased, 1.3 gr of ethyl benzoate was added at 110 ° C., and the mixture was kept at the same temperature for 1 hour. Thereafter, the solid was washed with purified toluene to obtain 5.5 gr of a solid catalyst component. The amount of supported Ti was 3.6% by weight.

(2) Polymerization of propylene A solid catalyst component 200 was placed in a 100 ml flask purged with purified N _2.
mgr and 10 ml of purified toluene were collected, 0.3 mmol of triethylaluminum was added with stirring, and the mixture was treated at room temperature for 1 hour.

In a 2 autoclave sufficiently purged with purified argon, place triethylaluminum at room temperature under an argon seal.
1.0 mmol, was added para-methyl methyl 0.3 mmol benzoic acid, further added so as with H ₂ in 1.0 kg / cm ² at room temperature,
700 gr of liquid propylene was charged. Next, after adding 9 mg of the treated catalyst component as a solid catalyst component, the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. As a result, the catalyst efficiency CE is
37,500 and the polymerization activity K was 1,250. The [rho _B was 0.47g / cc, II 97.5% is, MFI was 6.3.

The particle size distribution of the obtained polymer was such that 98% of the powder had a particle size of 400 μm to 150 μm, and the amount of fine powder of 100 μm or less was 0.1%, which was very narrow.

Example 7 (1) Production of catalyst component (A) A reaction product (a) was obtained in the same manner as in Example 1 (1).

After adding 87 ml of purified toluene thereto, the mixture was cooled to −20 ° C., and at −20 ° C., 24.8 gr of TiCl ₄ and SiCl ₃ (CH
₃ ) 6.5 gr was added. After the addition, the temperature was gradually raised. After the temperature was raised to 110 ° C., 1.3 g of ethyl benzoate was added, and the mixture was kept at the same temperature for 1 hour. Thereafter, the solid was washed with purified toluene to obtain a solid product.

This was followed by TiCl ₄ 82 gr and ethyl benzoate 1.3
After adding gr and treating the solid product at 80 ° C. for 1 hour, the solid product was sufficiently washed with purified toluene to obtain 5.0 gr of a solid catalyst component. The amount of supported Ti was 2.8% by weight.

(2) Polymerization of Propylene When propylene was polymerized in the same manner as in Example 1 (2), the catalyst efficiency CE was 54,000 g-pp / g-cat, and the polymerization activity K was 1,800. ρ _B is 0.43 g / cc and II is
97.0%, MFI was 6.2.

Also, the particle size distribution of the obtained polymer is very narrow, 400
The powder having a particle size of μm to 150 μm was 98% of the whole, and the amount of fine powder having a particle size of 100 μm or less was 0.1%.

Except that in Comparative Example 1 Example 1 (1) was not used SiCl ₃ (C ₆ H ₅₎ was in the same manner as in Example 1 (1) to obtain a solid catalyst component. When propylene polymerization was carried out using this product in the same manner as in Example 1 (2), the catalyst efficiency CE was 25,500 g.
-Pp / g-cat, and the polymerization activity K was 850. ρ _B is 0.42g /
cc, II was 96.6%, and MFI was 3.9.

Except that in Comparative Example -2 Example 2 (1) was used SiCl ₃ (C ₆ H ₅₎ was obtained was a solid catalyst component as in Example 2 (1). Propylene was polymerized in the same manner as in Example 1 (2) using this solid catalyst component.
Was 21,000 g-pp / g-cat, and the polymerization activity K was 700. Further, [rho _B is 0.41 g / cc, II is 97.0%, MFI was 4.5.

〔The invention's effect〕

According to the method of the present invention, an α-olefin polymer having excellent stereoregularity and particle properties can be obtained with extremely high polymerization activity, and is industrially useful.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating one embodiment of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/64-4/658

Claims (3)

(57) [Claims] (A) A compound of the general formula Mg (OR ⁴ ) _n (OR ⁵ ) _2-n (wherein R ⁴ and R ⁵ are an alkyl group, an aryl group or an aralkyl group, and R ⁴ and R ⁵ are the same. However, n may be 2
≥n> 0. A) a magnesium compound (a1) represented by the general formula Si (OR ⁶ ) _{4 wherein} R ⁶ is an alkyl group,
Indicates an aryl group or an aralkyl group. ) And, if necessary, a general formula Ti (OR ⁷ ) ₄
(Wherein, R ⁷ represents an alkyl group, an aryl group or an aralkyl group) and / or R ⁸ OH (in the period, R ⁸ represents an alkyl group, an aryl group or an aralkyl group). shows.) the heated reacted with the resulting component (a) a titanium tetrahalide (b), the general formula SiX _n R ³ _4-n
(Wherein, R ³ represents an alkyl group, an aryl group or an aralkyl group, X represents a halogen atom, n represents a number satisfying 4 ≧ n> 0) and an electron donor. Polymerizing or co-polymerizing an olefin having 3 or more carbon atoms in the presence of a solid catalyst component obtained by contact treatment with a reactive compound (d) and (B) a catalyst comprising an organometallic compound of a metal belonging to Group I to III of the periodic table. A method for producing an olefin polymer, comprising polymerizing. 2. The method according to claim 1, wherein component (a) contains at least one aryloxy group. 3. The method according to claim 1, wherein the olefin having 3 or more carbon atoms is polymerized or copolymerized in the presence of the electron donating compound (C).