JPH08176226A - Solid catalyst component for polymerization of olefin, catalyst for polymerization of olefin and production of olefin polymer - Google Patents

Abstract

PURPOSE: To obtain a solid catalyst for the polymerization of an olefin which can give a polymer excellent in particle properties by bringing a thermal reaction product among specified compounds into contact with a halogenated titanium compound, bringing the product of contact into contact with an electron-donating compound and treating the final product of contact under specified temperature conditions. CONSTITUTION: A halogenated titanium compound represented by the formula: TiXj (OR<5> )4-j (X is a halogen; R<5> is alkyl, aryl or the like; and j is in the range: 0<=j<=4) is added at 20 deg.C or below to a thermal reaction product among a magnesium compound represented by the formula: Mg(OR<1> )n (OR<2> )2-n (R<1> and R<2> are each alkyl, aryl or the like; and n is in the range: 0<=n<=2), a titanium compound represented by the formula: Ti(OR<3> )4-m Xm (R<3> is alkyl, aryl or the like; X is a halogen; and m is in the range: 0<=m<=4), a silicon compound represented by the formula: Si(OR<4> )4-k Xk (R<4> is alkyl, aryl or the like; X is a halogen; and k is in the range: 0<=k<=4) and optionally a compound represented by the formula: R<6> OH (wherein R<6> is alkyl, aryl or the like), the obtained mixture is brought into contact with an electron- donating compound, and the product of contact is heated at a temperature rising rate of 2.0 deg.C/min and treated at 110 deg.C or above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel solid catalyst component, an olefin polymerization catalyst, and a process for producing an olefin polymer using the same. Specifically, it gives an olefin polymer having excellent particle properties, and further, a solid catalyst component having excellent polymerization activity and stereoregularity, and an olefin polymerization catalyst comprising the solid catalyst component, an organic Al compound and an electron donating compound, And a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art There have been many proposals for a method for producing a supported catalyst which gives a highly stereoregular polymer with high activity to an olefin having 3 or more carbon atoms. However, many of them have polymerization activity,
All of the stereoregularity and the particle properties of the resulting polymer are not fully satisfied, and further improvement has been desired.

The inventors of the present invention previously disclosed Japanese Patent Laid-Open No. 64-5400.
No. 7, Mg alkoxide, Ti alkoxide,
And a reaction product of Si alkoxide with halogen-containing Ti
The solid catalyst component obtained by contacting the compound with an electron-donating compound is combined with an organometallic compound of Group I to III of the periodic table and, if necessary, an electron-donating compound to obtain a polymerization activity, Excellent stereoregularity,
Moreover, a method for producing a catalyst which gives a polymer having excellent particle properties has been proposed.

Further, in Japanese Patent Application Laid-Open No. 3-72503,
Mg alkoxide, Ti alkoxide, and Si
The reaction product of the alkoxide was mixed with the halogen-containing Ti compound.
General formula R _p(COO)_qM_rY_s(M = Ti, B, Ge)
By contact treatment with an electron-donating compound represented by
The solid catalyst component obtained by the above is added to the group I to III of the periodic table.
To combine organic metal compounds with electron-donating compounds
Has excellent polymerization activity, stereoregularity, and particle
A method for producing a catalyst which gives an excellent polymer is proposed.

In Japanese Patent Application No. 6-9353, Mg
The reaction product of alkoxide, Ti alkoxide, and Si alkoxide is treated with halogen-containing Ti at a temperature of 20 ° C. or lower.
After contacting the compound with an electron donating compound and heating the product at a temperature not exceeding 2.0 ° C./min, 110
By combining the solid catalyst component obtained by treating at a temperature higher than ℃ with an organometallic compound of Group I to III of the periodic table and an electron donating compound, the polymerization activity and stereoregularity are excellent, and the particles are A method for producing a catalyst that gives a polymer having excellent properties has been proposed.

By the way, of the catalyst manufacturing processes in these proposals, the contacting process with the halogen-containing Ti compound generally generates heat, so that the manufacturing equipment requires a cooling device such as a jacket heat exchanger. When the scale of production is increased by using a similar type reactor, the heat transfer area of the apparatus is relatively decreased, so unless steps are taken to reduce the temperature on the cooling device side or improve the heat transfer area, Takes more time. On the other hand, if the contacting process is carried out for a long time, the viscosity of the reaction solution may be increased or gelation may occur, resulting in poor stirring, poor heat removal, etc., so that a catalyst giving a polymer having excellent particle properties may not be obtained. .

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the polymerization activity, the stereoregularity, the polymer, and the like even when contacted with a halogen-containing Ti compound for a long time. The present invention has been accomplished by finding a catalyst that exhibits extremely high performance in all aspects of the particle properties of.

That is, the present invention provides (1) the general formula Mg (OR ¹ ) _n (OR ² ) _2-n (wherein
R ¹ and R ² represent an alkyl group, an aryl group or an aralkyl group, and R ¹ and R ² may be the same or different. n
Indicates 0 ≦ n ≦ 2. ) Mg compound (a
l), the general formula Ti (OR ³ ) _4-m X _m (wherein R ³ represents an alkyl group, an aryl group or an aralkyl group, X represents halogen, and m represents 0 ≦ m ≦ 4). Shown) and a Ti compound (a2) represented by the general formula Si (OR
⁴ ) _4-k X _k (In the formula, R ⁴ represents an alkyl group, an aryl group or an aralkyl group. X represents halogen.
k represents 0 ≦ k ≦ 4. ) Si compound (a
3), and optionally R ⁶ OH (wherein R ⁶
Is an alkyl group, an aryl group, an aralkyl group, or Si
The containing group is shown. ) A compound represented by (a4) the product obtained by heating the reaction (a *) of the general formula TiX _j (OR
⁵ ) _4-j (In the formula, X is halogen, R ⁵ is an alkyl group, an aryl group or an aralkyl group. J is 0 <j ≦ 4.
Indicates. ) A halogen-containing Ti compound (b *) represented by
To the electron donating compound (c *) before or after the end of the contact, and the contact product is kept at a temperature not exceeding 2.0 ° C / min. A solid catalyst component containing a solid (A *) obtained by heating at a temperature higher than 110 ° C. and then treating.

(2) A solid catalyst component for olefin polymerization obtained by contacting the following components (A *) to (C *). (A *) The solid (A *) described in claim (1). (B *) Organic Al compound. (C *) olefin.

(3) An olefin polymerization catalyst obtained by contacting the following components (A) to (C). (A) A solid catalyst component for olefin polymerization selected from (1) or (2). (B) Organic Al compound. (C) An electron-donating compound.

(4) Presence of the catalyst described in claim (3)
An olefin characterized by polymerizing an olefin in the presence of
Method for producing in-polymer. Exist in. Hereinafter, the present invention will be described in detail.
Explained. The general formula Mg (OR used in the present invention¹)_n
(OR²)_2-nAs a Mg compound (al) represented by
Is Mg (OCH₃)₂, Mg (OC₂H_Five)₂, Mg
(OC ₆H_Five)₂, Mg (OCH₂C₆H_Five)₂, Mg
(OC₂H_Five) (OC₆H_Five) Etc. dialkoxy mug
Nesium, Diaryloxymagnesium, Alkyl
Can include xylaryloxymagnesium
It Also, a plurality of these compounds can be used.

The compound (a2) represented by the general formula Ti (OR ³ ) _4-m X _m includes Ti (OCH ₃ ) ₄ and Ti
_{(OC 2 H 5) 4,} Ti alkoxy titanium such as _{(O-n-C 4 H} 9) 4, Ti (OC 2 H 5) 3 Cl, Ti
_{(O-n-C 4 H} 9) 3 Cl, Ti (O-n-C
₄ H ₉₎ and halogen-containing alkoxy titanium such as ₂ Cl _2. Also, a plurality of these compounds can be used.

As the compound (a3) represented by the general formula Si (OR ⁴ ) _4-k X _k , Si (OCH ₃ ) ₄ ,
_{Si (OC 2 H 5) 4} , Si (O-n-C 4 H 9) 4,
Alkoxysilanes such as Si (OC ₆ H ₅ ) ₄ and aryloxysilanes, Si (OC ₂ H ₅ ) ₃ Cl, Si
_{(O-n-C 4 H} 9) 3 Cl, Si (OC 6 H 5) 3 C
There may be mentioned halogen-containing alkoxysilanes such as 1 and halogen-containing aryloxysilanes. Also,
A plurality of these compounds can be used.

Compound (a4) represented by the general formula R ⁶ OH
As, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, cyclohexanol, benzyl alcohol, silanols such as trimethylsilanol, triphenylsilanol, phenol, cresol, xylenol, butylphenol and the like. Mention may be made of phenols. It is preferable that any of these compounds (a1) to (a4) contains an aryloxy group. Also, a plurality of these compounds can be used.

Mg compound (a1), Ti compound (a
2), Si compound (a3) and, if necessary, ROH
There are no particular restrictions on the reaction sequence for obtaining the reaction product (a *) of (a4). In addition, an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene, xylene may be present during the reaction. The reaction temperature is 60 to 250 ° C., preferably 100 to 180 ° C., and the reaction time is about 0.5 to 4 hours.

The amounts of (a1) to (a4) used are usually as follows. (A1) :( a2) :( a3) :( a4) = 1: 0.05-4: 0.05-5: 0-5 The reaction product (a *) of (a1)-(a4) is (A1)
From (a4) to (a4), it is possible to obtain a liquid material by the composition ratio of each component.

In the present invention, the reaction product (a *) obtained as described above is brought into contact with the halogen-containing titanium compound (b *) by adding the electron-donating compound (c *). Raise the temperature below. The contact method of (c *) is not particularly limited, but (c *) is added to (a *).
The method of contacting (c *) with (b *) in advance, the method of contacting (c *) with the reaction products of (a *) and (b *), and the like are used. Electron donating compound (c *)
The contact with (a *) or (b *) can be carried out in the presence or absence of an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene or xylene. The contact temperature is also not particularly limited, but is usually in the range of -50 ° C to 200 ° C, preferably -40 ° C to 50 ° C.

The amount of (c *) used is not particularly limited, but the usual amount used is represented by the following molar ratio to Mg in (a *). As the compound used as Mg: (c *) = 1: 0.01 to 2 (c *), an oxygen-containing compound and a nitrogen-containing compound can be generally cited.

As the nitrogen-containing compound, (C ₂ H ₅ )
_{3 N, H 2 N (CH} 2) 2 NH 2, (i-C 3 H 7) 2
_{NH, (t-C 4 H} 9) 2 NH, pyridine, piperidine, amines and derivatives thereof such as 2,2,6,6-tetramethylpiperidine also, tertiary amines, pyridines, the quinolines N Mention may be made of nitroso compounds such as -oxides.

As the oxygen-containing compound, ethers, ketones, esters and alkoxysilanes can be generally mentioned. Examples of ethers include diethyl ether, dipropyl ether, diethylene glycol, dimethyl ether, propylene glycol dimethyl ether, ethylene oxide, tetrahydrofuran, 2,2,2.
5,5-tetramethyltetrahydrofuran, dioxane and the like, ketones such as acetone, diethyl ketone, methyl ethyl ketone and acetophenone, and esters such as ethyl phenylacetate, methyl benzoate, ethyl benzoate, phenyl benzoate and toluyl. Methyl acid, ethyl toluate, methyl anisate, ethyl anisate, methyl methoxybenzoate, ethyl methoxybenzoate, methyl methacrylate, ethyl methacrylate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate,
Alkoxysilanes such as dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, γ-butyrolactone and ethyl cellosolve can be used as the alkoxysilanes. Methoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, t-
Butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltri Ethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane,
Cyclohexyltriethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, diphenyldiethoxysilane, t
-Butylmethyldiethoxysilane, cyclohexylmethyldiethoxysilane and the like can be mentioned.

Of these, preferably used is
Esters and alkoxysilanes are preferable, and esters are more preferable. Among the esters, carboxylic acid esters are more preferably used, phthalic acid esters are particularly preferred, and diethyl phthalate is most preferred. In the present invention, the contact product (a *) is contacted by adding it to the halogen-containing titanium compound (b *), and then heated to treat the component (A *). At this time, (a *) or (b *) divides the predetermined amount into a plurality of times,
You may add and contact alternately or continuously.

As the halogen-containing titanium compound (b *) used here, TiCl ₄ , TiBr ₄ , and Til _{4 are used.}
Titanium tetrahalides, such as, Ti (O-n-C 4 H
₉ ) Halogen-containing alkoxy titanium such as Cl ₃ and Ti (OC ₆ H ₅ ) Cl ₃ , halogen-containing aryloxy titanium and the like can be mentioned. Further, as the halogen-containing alkoxytitanium, a mixture of a plurality of (b *) components at an arbitrary ratio prior to the contacting step may be used. For example, TiCl _Y (OBu) _(4-Y) (0 ≦ Y where TiCl ₄ and Ti (OBu) ₄ are mixed and contacted at an arbitrary ratio.
A component (b *) represented by a composition such as ≦ 4) can also be used. For the production of a catalyst that gives a polymer with a small amount of fine powder, it is preferable to use alkoxy titanium containing halogen at least in part rather than using titanium tetrahalide.

In the step of contacting the reaction product (a *) with the halogen-containing titanium compound (b *), the use of an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene and xylene is optional. However, it is usually better to use a solvent with a somewhat higher boiling point, such as toluene,
It is convenient in the manufacturing process. The contact is carried out at a temperature of 20 ° C. or lower, preferably −80 to 10 ° C., more preferably −50 to
It is carried out in the range of 0 ° C. When the contact temperature is lowered as described above, the contact product is likely to be a uniform liquid, and by heating and heating the uniform liquid to precipitate a solid, a solid catalyst component having particularly good particle properties can be obtained. .

The amount of (b *) used is not particularly limited, but it is usually used in the following range as a molar ratio to Mg in (a *). Mg: (b *) = 1: 0.5 to 20 In the present invention, after the contact is performed, 2.0 ° C./m
The component (A *) is obtained by increasing the temperature under conditions not exceeding in, preferably 1.0 ° C./min, and further treating at temperatures exceeding 110 ° C. here,
The average heating rate is the difference between the contact temperature and the maximum temperature required for the treatment divided by the time required for raising the temperature. The temperature rise does not necessarily have to be performed uniformly, and a step of achieving a constant temperature may be provided during the process. By reducing the average heating rate in this way, it becomes possible to obtain a catalyst having excellent particle properties in terms of bulk density, particle size distribution, and fine powder amount.

The maximum temperature is higher than 110 ° C., but if the temperature is too high, unfavorable results such as a decrease in activity may occur. Therefore, the treatment is usually performed at a temperature higher than 110 ° C. and lower than 170 ° C. It is normal to do.
Although there is no limitation on the time required for one treatment described above, it is usually performed in the range of 0.5 to 12 hours. Also, (b
The treatment by *) may be performed multiple times. In the second and subsequent processes, the temperature rising rate is arbitrary.

After the above treatment, it is washed with an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, toluene and xylene to obtain a slurry of component (A *). The preferred combinations for obtaining the (A *) component having high performance as an olefin polymerization catalyst are as follows.

(A1): Mg (OR) ₂ (R: alkyl group or aryl group) (a2): Ti (OR) ₄ (R: alkyl group) (a3): Si (OR) ₄ (R: aryl group) And / or alkyl group) (a4): ROH (R: aryl group) (c *): phthalic acid diester (b *): TiCl _j (OR) _4-j (0 <j ≦ 4; R:
Alkyl group or aryl group)

The component (A *) can be directly supplied to the reactor as a solid catalyst component (A) to obtain an olefin polymer. However, in order to obtain good powder properties, the solid catalyst component (A) is newly added by bringing the component (A *) into contact with the organic Al compound (B *) and the olefin (C *) in advance. Are preferably formed.

As the component (B *) used here, trimethyl aluminum, triethyl aluminum, tri-
Trialkylaluminums such as n-propylaluminum and triisobutylaluminum, halogen-containing organoaluminum compounds such as diethylaluminum chloride and sesquialuminum chloride, hydride-containing organoaluminum compounds such as diethylaluminum hydride, dimethylaluminum methoxide and diethyl. Examples thereof include alkoxide-containing organic aluminum compounds such as aluminum methoxide and diethylaluminum phenoxide, and aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. Also, a plurality of these may be used. The component (B *) has a molar ratio of Al in the component (B *) to Ti in the component (A *) of 0.1.
It is used so as to be ~ 100.

As the olefin used as the component (C *), those having a carbon-carbon double bond which can be polymerized by a Ziegler catalyst can be used. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, styrene, Examples thereof include α-olefins such as divinylbenzene, internal olefins such as 2-butene, 2-pentene, cyclopentene, and cyclohexene. These may be used alone,
You may use it as a mixture. The amount of (C *) is (A *)
The amount is 0.1 to 1000 times, preferably 0.5 to 300 times, more preferably 0.5 to 50 times, and particularly preferably 1 to 3 times.

The above contact can be suitably carried out in an inert hydrocarbon solvent such as butane, pentane, hexane, heptane and toluene, but it may be carried out in the substantial absence of a solvent. The method of contacting each of the components (A *), (B *) and (C *) is arbitrary. That is, they may be contacted at the same time, or each component may be contacted sequentially. The contact temperature is −20 ° C. to 130 ° C., preferably 0 ° C. to 70 ° C. Further, the contact may be of a batch type or a continuous type.

An olefin polymerization catalyst can be obtained by bringing the above solid catalyst component (A) into contact with the organoaluminum compound (B) and the electron donating compound (C).
As the organoaluminum compound used as the component (B), the same compounds as the above-mentioned component (B *) can be used. The component (B) and the component (B *) may be the same or different.

The amount of the component (B) used is not particularly limited,
It is used so that the molar ratio of Al in the component (B) and Ti in the component (A) is 1 to 5000, preferably 50 to 1000. As the electron donating compound used as the component (C), the same compounds as the component (c *) can be used. Here, the component (C) and the component (c *) may be the same or different. Of the compounds that can be used as the component (C), preferably used are piperidines,
Carboxylic acid esters or alkoxysilanes, particularly preferably alkoxysilanes.

There is no limitation on the amount of the component (C) used, but normally, the molar ratio to Al in the component (B) is 0.001 to 0.001.
It is used so as to be 10, preferably 0.01 to 2. For the polymerization of olefins, a commonly used method can be adopted. For example, a method of carrying out the polymerization in the liquid phase in the presence of an inert hydrocarbon solvent, a method of carrying out the liquefied olefin itself as a medium, a method of carrying out the polymerization in the gas phase under the condition that the liquid phase does not substantially exist, etc. To be Further, the polymerization may be either batch type or continuous type.

The olefin used for the polymerization is carbon-
Any olefin having a carbon double bond can be used. Specifically, ethylene, propylene, 1
-Butene, 1-pentene, 1-hexene, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
Examples thereof include α-olefins such as 1-pentene, vinylcyclohexane and styrene, internal olefins such as 2-butene, 2-pentene, cyclopentene and cyclohexene, Si-containing olefins such as vinylsilane and allylsilane. These may be used alone or as a mixture. Of these olefins, α-olefins are particularly preferably used.

When an α-olefin having 3 or more carbon atoms is used among the α-olefins, a polymer having a high stereoregularity can be obtained. Especially, when propylene is used, extremely high isotacticity can be obtained. The reaction conditions are usually 1 to 100 atm, preferably 5 to 40 atm, usually 40 to 120 ° C,
It is preferably carried out in the range of 50 to 90 ° C. Further, as a method for adjusting the molecular weight of the produced polymer, a known molecular weight adjusting agent such as hydrogen or diethyl zinc can be appropriately added.

[0037]

The present invention will be described below with reference to examples.
The present invention is not limited to this without departing from the gist thereof. In the examples, the polymerization activity K is 1 kgf / cm of polymerization monomer pressure per hour.
² is the amount of polymer produced (g) per 1 g of (A *). Moreover, MFR was measured according to ASTM-D-1238.

The amount of xylene-insoluble component (II _oXYL ) as a measure of _{stereoregularity} was measured by the following method.
About 1 g of a polypropylene powder sample was precisely weighed in an eggplant-shaped flask, 200 mL of xylene was added thereto, and the mixture was heated to boiling and completely dissolved. Then, this was rapidly cooled in a water bath, the precipitated solid portion was filtered, and 50 mL of the filtrate was evaporated to dryness in a platinum dish and further dried under reduced pressure, and the weight was weighed. II
_oXYL was calculated as the amount of xylene-insoluble components in the polypropylene powder sample.

The bulk density (ρ _B ) is JIS-K-672.
It was measured according to 1. The particle size distribution of the polymer was measured using a standard sieve manufactured by Mitamura Riken Co., Ltd.
The slope of the mmler plot was defined as the n term, which was used as a measure of the particle size distribution. Further, the fraction less than 106μ was made into a fine powder and expressed in% by weight. The following catalyst production process and polymerization process were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated with MS-4A and then deaerated by bubbling with purified nitrogen.

Example 1 (1) Production of Solid Catalyst Component (A) A 500 mL-tank type flask equipped with a vacuum stirrer was charged with 36.9 g of Mg (OEt) ₂ :
Ti (OBu) ₄ : 50.8 g was charged and the temperature was raised with stirring.

After reacting for 1 HR at 150 ° C., 0.96
A toluene solution of Si (OPh) ₄ diluted to 5 mol / L: 169 mL was added dropwise, the reaction was continued at 120 ° C. for 1 hour, and then the temperature was lowered to room temperature. Furthermore, Si (OE
t) ₄ : 14.7 g and diethyl phthalate: 7.2 g were added, and the mixture was diluted with toluene: 214.7 mL to obtain (a *).

Ti (OBu) ₄ : 3.43 g and toluene: 63.6 mL were charged to another 500 mL tank flask equipped with a vacuum stirrer and baffles. Thereafter, the temperature was cooled to -5 ℃, TiCl _{4: 4}
7.8g was added. Subsequently, with stirring at 300 rpm, 63 mmol of (a *) as Mg was added dropwise over 120 minutes to obtain a uniform solution. At this time, the viscosity of the solution was slightly increased, and gelation did not occur. This homogeneous solution was heated to 15 ° C. for 20 minutes and reacted at 15 ° C. for 1 hour, then heated to 117 ° C. for 1 hour and reacted for 1 hour.

After completion of the treatment, heating / stirring was stopped, the supernatant was removed, and the mixture was washed 3 times with 150 mL of toluene,
A solid slurry was obtained. Next, the toluene amount of the obtained solid slurry was adjusted to 210 mL, and Ti was added at room temperature.
Cl _4: 34.6mL was added. Add this slurry to 3
The temperature was raised with stirring at 00 rpm, and the reaction was carried out at 115 ° C. for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant was removed, and then washed with toluene: 150 mL three times,
A toluene slurry of (A *) was obtained. The obtained slurry contained 6.87 g of (A *). Next, a part of the slurry obtained here was charged into another 500 mL tank type flask equipped with a vacuum stirrer as a component (A *) of 270 mg. After adding 100 mL of n-hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition is complete
The mixture was slowly stirred at room temperature for 30 minutes, and then propylene gas was passed through the gas phase for 45 seconds.
During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The solid catalyst component (A) thus obtained is (A *) component: 1
It contained 2.0 g of propylene polymer per gram.

(2) Polymerization of Propylene An induction stirring type 2L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.2 mmol of cyclohexylmethyldimethoxysilane at room temperature under a nitrogen stream. Furthermore, hydrogen was added to 0.5 kgf / cm ² , and 750 g of liquid propylene was charged.

The temperature was raised to 70 ° C. with stirring, and when the temperature reached 70 ° C., 10.8 mg of the solid catalyst component obtained in Example 1 (1) was added as the component (A *) to carry out polymerization. Started. After polymerization was carried out at 70 ° C. for 1 hour, excess propylene was purged to terminate the polymerization. The obtained propylene polymer was 290 g. Polymerization activity K = 895, II
_{oX YL} = 98.0%, ρ _B = _{0.46 g} / cc, MFR =
The value was 10.8 g / 10 min and the n term was 9.2. The fine powder was 0.01 wt%.

Example 2 (1) Production of Solid Catalyst Component (A) A 500 mL-tank type flask equipped with a Baquium stirrer was charged with Mg (OEt) ₂ : 36.9 g, and then,
Ti (OBu) ₄ : 50.8 g was charged and the temperature was raised with stirring.

After reacting for 1 HR at 150 ° C., 0.96
A toluene solution of Si (OPh) ₄ diluted to 5 mol / L: 169 mL was added dropwise, the reaction was continued at 120 ° C. for 1 hour, and then the temperature was lowered to room temperature. Furthermore, Si (O
Et) ₄ : 14.7 g, diethyl phthalate: 7.2 g were added, and diluted with toluene: 214.7 mL (a *).
I got

Ti (OBu) ₄ : 3.39 g and toluene: 65.0 mL were charged to another 500 mL tank flask equipped with a vacuum stirrer and baffles. Thereafter, the temperature was cooled to -5 ℃, TiCl _4: 1
8.0 g was added. Subsequently, while stirring at 300 rpm, 63.4 mmol of (a *) as Mg was added to 12
It was dripped in 0 minutes. Further, 30.1 g of TiCl _{4 was} added dropwise to obtain a uniform solution. At this time, the viscosity of the solution was slightly increased, and gelation did not occur. 20 this homogeneous solution
After raising the temperature to 15 ° C in a minute and reacting at 15 ° C for 1 hour,
The temperature was raised to 117 ° C. in 1 hour and the reaction was carried out for 1 hour.

After completion of the treatment, heating / stirring was stopped, the supernatant liquid was removed, and then washed with toluene: 150 mL three times,
A solid slurry was obtained. Next, the toluene amount of the obtained solid slurry was adjusted to 210 mL, and Ti was added at room temperature.
Cl _4: 34.8mL was added. Add this slurry to 3
The temperature was raised with stirring at 00 rpm, and the reaction was carried out at 115 ° C. for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant was removed, and then washed with toluene: 150 mL three times,
A toluene slurry of (A *) was obtained. The resulting slurry contained 7.86 g of (A *). Next, a part of the slurry obtained here was charged into another 500 mL tank type flask equipped with a vacuum stirrer as a component (A *) of 270 mg. After adding 100 mL of n-hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition was completed, the mixture was slowly stirred at room temperature for 30 minutes. Then
Propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The obtained solid catalyst component (A) contained 1.8 g of propylene polymer per 1 g of component (A *).

(2) Polymerization of Propylene An induction stirring type 2 L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.2 mmol of cyclohexylmethyldimethoxysilane at room temperature under a nitrogen stream. Furthermore, hydrogen was added to 0.5 kgf / cm ² , and 750 g of liquid propylene was charged.

While stirring, the temperature was raised to 70 ° C. until it reached 70 ° C.
At that time, the solid catalyst component obtained in Example 1 (1)
Was added as component (A *) to start the polymerization.
Started After polymerization was carried out at 70 ° C for 1 hour, excess propylene was added.
The polymerization was stopped by purging the len. Propylene obtained
The amount of the polymer was 404 g. Polymerization activity K = 1150,
II _oXYL= 98.2%, ρ_B= 0.44 g / cc, MFR
= 10.0 g / 10 min, n-term = 8.7. Well
The fine powder was 0.05 wt%.

Example 3 (1) Production of Solid Catalyst Component (A) A 500 mL-tank type flask equipped with a vacuum stirrer was charged with 45.1 g of Mg (OEt) ₂ :
Ti (OBu) ₄ : 81.4 g was charged and the temperature was raised with stirring.

After reacting for 1 HR at 150 ° C., 0.95
205 mL of a toluene solution of Si (OPh) ₄ diluted to 9 mol / L was added dropwise, followed by reaction at 120 ° C. for 1 hour, and then cooled to room temperature. Furthermore, Si (O
Et) ₄ : 17.3 g and diethyl phthalate: 8.8 g were added and diluted with toluene: 21.3 mL to obtain (a *).

Toluene: 96.6 mL of vacuum
Charge to another 500 mL tank flask equipped with stirrer and baffle. After this, cool the temperature to -5 ° C,
TiCl _4: 16.1g was added. Continue to 300
While stirring at rpm, 56.5 mmol of (a *) as Mg was added dropwise over 120 minutes, and TiCl ₄ :
26.8 g was added to obtain a uniform solution. At this time, the viscosity of the solution was slightly increased, and gelation did not occur. This homogeneous solution was heated to 15 ° C. for 20 minutes and reacted at 15 ° C. for 1 hour, then heated to 117 ° C. for 1 hour and reacted for 1 hour.

After completion of the treatment, heating / stirring was stopped, the supernatant liquid was removed, and then washed with toluene: 150 mL three times,
A solid slurry was obtained. Next, the toluene amount of the obtained solid slurry was adjusted to 210 mL, and Ti was added at room temperature.
Cl _4: 34.6g was added. Add this slurry to 30
The temperature was raised with stirring at 0 rpm, and the reaction was carried out at 115 ° C. for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant liquid was removed, and then washed with toluene: 150 mL three times,
A toluene slurry of (A *) was obtained. The resulting slurry contained 7.63 g of (A *). Next, a part of the slurry obtained here was charged into another 500 mL tank type flask equipped with a vacuum stirrer as a component (A *) (270 mg). After adding 100 mL of n-hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition is complete
The mixture was slowly stirred at room temperature for 30 minutes. Then, propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The obtained solid catalyst component (A) is (A *) component per 1 g,
It contained 2.3 g of propylene polymer.

(2) Polymerization of Propylene An induction stirring type 2 L-autoclave was charged with triethylaluminum: 2.0 mmol and cyclohexylmethyldimethoxysilane: 0.2 mmol at room temperature under a nitrogen stream. Furthermore, hydrogen was added to 0.5 kgf / cm ² , and 750 g of liquid propylene was charged.

While stirring, the temperature was raised to 70 ° C. until it reached 70 ° C.
At that time, the solid catalyst component obtained in Example 1 (1)
To 11.4 mg as component (A *) to start the polymerization.
Started After polymerization was carried out at 70 ° C for 1 hour, excess propylene was added.
The polymerization was stopped by purging the len. Propylene obtained
The amount of the polymer was 389 g. Polymerization activity K = 1137,
II _oXYL= 97.6%, ρ_B= 0.43 g / cc, MFR
= 14.3 g / 10 min, n-term = 6.2. Well
The fine powder was 1.76 wt%.

Example 4 (1) Production of Solid Catalyst Component (A) Mg (OEt) ₂ : 27.2 g was charged into a 500 mL-tank type flask equipped with a vacuum stirrer, and then T
i (OBu) ₄ : 50.1 g was charged and the temperature was raised with stirring.

After reacting for 1 HR at 150 ° C., 0.95
A toluene solution of Si (OPh) ₄ diluted to 4 mol / L: 129 mL was added dropwise, followed by reaction at 120 ° C. for 1 hour, and then cooled to room temperature. Furthermore, Si (OE
t) ₄ : 10.4 g and diethyl phthalate: 5.3 g were added and diluted with toluene: 166.8 mL to obtain (a *).

3.05 g of Ti (OBu) ₄ and 65.3 mL of toluene were charged to another 500 mL tank flask equipped with a vacuum stirrer and baffles. Thereafter, the temperature was cooled to -5 ℃, TiCl _4: 1
7.1 g was added. Then, while stirring at 300 rpm, 12 of 60.1 mmol of (a *) as Mg was added.
The mixture was added dropwise over 0 minutes, and TiCl ₄ : 28.5 g was added to obtain a uniform solution. This homogeneous solution is heated to 15 ° C for 20 minutes.
Up to 11 ° C for 1 hour
The temperature was raised to 7 ° C. and the reaction was performed for 1 hour.

After completion of the treatment, heating / stirring was stopped, the supernatant was removed, and the mixture was washed 3 times with 150 mL of toluene,
A solid slurry was obtained. Next, the toluene amount of the obtained solid slurry was adjusted to 200 mL, and Ti was added at room temperature.
Cl _4: 33.0mL was added. Add this slurry to 3
The temperature was raised with stirring at 00 rpm, and the reaction was carried out at 115 ° C. for 1 hour.

After completion of the reaction, heating / stirring was stopped, the supernatant was removed, and the mixture was washed 3 times with 150 mL of toluene,
A toluene slurry of (A *) was obtained. The obtained slurry contained 5.7 g of (A *). Next, a part of the slurry obtained here was charged into another 500 mL tank type flask equipped with a vacuum stirrer as a component (A *) of 270 mg. After adding 100 mL of n-hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition is complete
The mixture was slowly stirred at room temperature for 30 minutes. Then, propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The obtained solid catalyst component (A) is (A *) component per 1 g,
It contained 2.5 g of propylene polymer.

(2) Polymerization of Propylene An induction stirring type 2 L-autoclave was charged with triethylaluminum: 2.0 mmol and cyclohexylmethyldimethoxysilane: 0.2 mmol in a nitrogen stream at room temperature. Furthermore, hydrogen was added to 0.5 kgf / cm ² , and 750 g of liquid propylene was charged.

While stirring, the temperature was raised to 70 ° C. until it reached 70 ° C.
At that time, the solid catalyst component obtained in Example 1 (1)
To 11.4 mg as component (A *) to start the polymerization.
Started After polymerization was carried out at 70 ° C for 1 hour, excess propylene was added.
The polymerization was stopped by purging the len. Propylene obtained
The amount of the polymer was 375 g. Polymerization activity K = 1097,
II _oXYL= 98.3%, ρ_B= 0.47 g / cc, MFR
= 9.0 g / 10 min, n-term = 9.5. Also
The fine powder was 0.07 wt%.

Comparative Example 1 (1) Production of solid catalyst component (A) A solid catalyst component was produced in the same manner as in Example 1 except that the order of addition of TiCl ₄ and (a *) was reversed. It was TiCl ₄ was added so that the temperature of the reaction solution was kept at −5 ° C. The time required to add TiCl ₄ was 120 min. As a result, the viscosity of the entire reaction solution increased during the addition of TiCl ₄ and a gel was formed.

Comparative Example 2 (1) Production of Solid Catalyst Component (A) A solid catalyst component was produced under the same conditions as in Example 1 except that the addition temperature of (a *) was 30 ° C. .
The slurry obtained here contained 6.98 g of (A *).

Next, a part of the slurry obtained here is
Into another 500 mL tank type flask equipped with a vacuum stirrer, 270 mg was charged as the component (A *). n-
After adding 100 mL of hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition was completed, the mixture was slowly stirred at room temperature for 30 minutes. Then, propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C.
After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The solid catalyst component (A) thus obtained is (A
*) Component: 2.3 g of propylene polymer was contained per 1 g.

(2) Polymerization of Propylene An induction stirring type 2L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.1 mmol of phenyltrimethoxysilane under a nitrogen stream at room temperature. Furthermore, hydrogen was added to 0.9 kgf / cm ² ,
750 g of liquid propylene was charged.

While stirring, the temperature was raised to 70 ° C. until it reached 70 ° C.
At that time, the solid catalyst component obtained in Comparative Example 2 (1)
10.8 mg as a component (A *) was added to initiate the polymerization.
Started After polymerization was carried out at 70 ° C for 1 hour, excess propylene was added.
The polymerization was stopped by purging the len. Propylene obtained
The amount of the polymer was 340 g. Polymerization activity K = 1050,
II _oXYL= 98.1%, ρ_B= 0.33 g / cc, MFR
= 8.9 g / 10 min, n-term = 1.7. Also
The fine powder was 23.0 wt%.

Comparative Example 3 (1) Production of Solid Catalyst Component (A) Solid conditions were the same as in Example 1 except that the temperature rising time up to 15 ° C. after addition of (a *) was 8 minutes. A catalyst component was produced. The slurry obtained here is (A
It contained 6.80 g of *).

Next, a part of the slurry obtained here is
Into another 500 mL tank type flask equipped with a vacuum stirrer, 270 mg was charged as the component (A *). n-
After adding 100 mL of hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition was completed, the mixture was slowly stirred at room temperature for 30 minutes. Next, propylene gas was added to the vapor phase 45
Circulated for seconds. During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The obtained solid catalyst component (A) is
Component (A *) contained 2.6 g of propylene polymer per 1 g.

(2) Polymerization of Propylene An induction stirring type 2L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.1 mmol of phenyltrimethoxysilane under a nitrogen stream at room temperature. Furthermore, hydrogen was added to 0.9 kgf / cm ² ,
750 g of liquid propylene was charged.

The temperature was raised to 70 ° C. with stirring, and when the temperature reached 70 ° C., 11.0 mg of the solid catalyst component obtained in Comparative Example 3 (1) was added as the component (A *) to carry out polymerization. Started. After polymerization was carried out at 70 ° C. for 1 hour, excess propylene was purged to terminate the polymerization. The obtained propylene polymer was 304 g. Polymerization activity K = 920, II
_{oX YL} = 98.0%, ρ _B = 0.42 g / cc, MFR =
It was 11.5 g / 10 min and the n term was 4.2. The fine powder was 1.1 wt%.

Comparative Example 4 (1) Production of Solid Catalyst Component (A) Solid catalyst component was prepared under the same conditions as in Example 1 except that the reaction temperature after reacting at 15 ° C. for 1 hour was 110 ° C. Was manufactured. The slurry obtained here is (A
It contained 7.10 g of *).

Next, a part of the slurry obtained here is
Into another 500 mL tank type flask equipped with a vacuum stirrer, 270 mg was charged as the component (A *). n-
After adding 100 mL of hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition was completed, the mixture was slowly stirred at room temperature for 30 minutes. Then, propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C. After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The obtained solid catalyst component (A) is
(A *) component: 2.5 g of propylene polymer was contained per 1 g.

(2) Polymerization of Propylene An induction stirring type 2 L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.1 mmol of phenyltrimethoxysilane in a nitrogen stream at room temperature. Furthermore, hydrogen was added to 0.9 kgf / cm ² ,
750 g of liquid propylene was charged.

The temperature was raised to 70 ° C. with stirring, and when the temperature reached 70 ° C., 10.0 mg of the solid catalyst component obtained in Comparative Example 4 (1) was added as the component (A *) to carry out polymerization. Started. After polymerization was carried out at 70 ° C. for 1 hour, excess propylene was purged to terminate the polymerization. The obtained propylene polymer was 278 g. Polymerization activity K = 928, II
_{oX YL} = 97.3%, ρ _B = 0.45 _g / cc, MFR =
The value was 12.8 g / 10 min and the n term was 8.8. The fine powder was 0.02 wt%.

Comparative Example 5 (1) Production of Solid Catalyst Component (A) Solid catalyst component was prepared under the same conditions as in Example 1 except that the reaction temperature after reacting at 15 ° C. for 1 hour was 90 ° C. Was manufactured. The slurry obtained here is (A
It contained 7.20 g of *).

Next, a part of the slurry obtained here is
Into another 500 mL tank type flask equipped with a vacuum stirrer, 270 mg was charged as the component (A *). n-
After adding 100 mL of hexane, 0.42 mmol of triethylaluminum was added at room temperature while slowly stirring. After the addition was completed, the mixture was slowly stirred at room temperature for 30 minutes. Then propylene gas was passed through the gas phase for 45 seconds. During this period, the temperature was kept at 20 ° C.
After the completion, the flow of propylene gas was stopped to obtain a solid catalyst component (A). The solid catalyst component (A) thus obtained is (A
*) Component: It contained 2.2 g of propylene polymer per 1 g.

(2) Propylene Polymerization An induction stirring type 2L-autoclave was charged with 2.0 mmol of triethylaluminum and 0.1 mmol of phenyltrimethoxysilane under a nitrogen stream at room temperature. Furthermore, hydrogen was added to 0.9 kgf / cm ² ,
750 g of liquid propylene was charged.

While stirring, the temperature was raised to 70 ° C. until it reached 70 ° C.
At that time, the solid catalyst component obtained in Comparative Example 5 (1)
Is added as a component (A *) to start the polymerization.
Started After polymerization was carried out at 70 ° C for 1 hour, excess propylene was added.
The polymerization was stopped by purging the len. Propylene obtained
The amount of the polymer was 363 g. Polymerization activity K = 1100,
II _oXYL= 96.8%, ρ_B= 0.44 g / cc, MFR
= 13.7 g / 10 min, and n term was 9.4. Well
The fine powder was 0.01 wt%.

[0085]

EFFECTS OF THE INVENTION According to the method of the present invention, when a polymer of α-olefin, particularly a polymer of propylene, is produced on a large scale, it has a good powder property in addition to high activity and stereoregularity. The obtained polymer is industrially useful.

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuro Tamaki, 3-10-10 Shiodotsu, Kurashiki-shi, Okayama Mitsubishi Chemical Corporation Mizushima Development Laboratory

Claims (4)

[Claims] 1. The general formula Mg (OR¹)_n(OR²)_2-n
(In the formula, R¹, R²Is an alkyl group, an aryl group or
Represents an aralkyl group, R¹And R²Are the same or different
Good. n represents 0 ≦ n ≦ 2. ) Mg compound represented by
Thing (a1), general formula Ti (OR³)_4-mX_m(In the formula, R
³Represents an alkyl group, an aryl group or an aralkyl group.
You. X represents halogen. m indicates 0 ≦ m ≦ 4
You. ) Ti compound (a2) represented by
i (OR^Four)_4-kX_k(In the formula, R ^FourIs an alkyl group, ant
Group or aralkyl group. X is a halogen
Is shown. k represents 0 ≦ k ≦ 4. ) Si conversion represented by
Compound (a3) and, if necessary, the general formula R⁶OH (formula
Medium, R⁶Is an alkyl group, aryl group, aralkyl group, or
Or represents a Si-containing group. ) The compound (a4)
The product (a *) obtained by heating and reacting is represented by the general formula TiX.
_j(OR^Five)_4-j(In the formula, X is halogen, R ^FiveIs al
A kill group, an aryl group or an aralkyl group is shown. j is
0 <j ≦ 4 is shown. ) A halogen-containing Ti compound represented by
When added to the product (b *) at a temperature of 20 ° C or less,
The electron donating compound (c
*) And then contacting the product with 2.0 ° C / m
After raising the temperature under conditions not exceeding in, the temperature exceeding 110 ° C
Includes solid (A *) obtained by treatment
Solid catalyst component. 2. A solid catalyst component for olefin polymerization obtained by bringing the following components (A *) to (C *) into contact with each other. (A *) The solid (A *) described in claim (1). (B *) Organic Al compound. (C *) olefin. 3. A catalyst for olefin polymerization obtained by bringing the following components (A) to (C) into contact with each other. (A) A solid catalyst component for olefin polymerization selected from (1) or (2). (B) Organic Al compound. (C) An electron-donating compound. 4. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the catalyst according to claim 3.