JPH09124724A - Olefin polymerization catalyst and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which is suitable for a vapor phase polymn. and provides a highly stereoregular olefin polymer at a high polymn. activity by compounding an organoaluminum compd. with a solid catalyst component obtd. by specifically treating an Mg compd.-alcohol mixture, a halogenated titanium compd., and an electron donor. SOLUTION: This catalyst comprises a solid catalyst component, an organoaluminum compd., and if necessary an electron donor. The solid catalyst component is prepd. under specified conditions by spraying an Mg compd.- alcohol mixture in the molten state in a spray tower which is cooled to such an inside temp. that a solid component is obtd. without causing an alcohol to evaporate, partly removing the alcohol from the solid component, and bringing it into contact with a halogenated titanium compd. and an electron donor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer. More specifically, a solid catalyst component suitable for gas-phase polymerization, having a relatively large particle size and a spherical shape, and having excellent crush resistance during polymerization,
The present invention relates to a catalyst for olefin polymerization, which comprises an organoaluminum compound and, if necessary, an electron donor, and a method for producing an olefin polymer, which comprises (co) polymerizing an olefin in the presence of the catalyst.

[0002]

2. Description of the Related Art As a solid catalyst component for olefin polymerization, a so-called supported solid catalyst component having a magnesium compound as a carrier has been known in recent years, and a number of techniques exhibiting excellent polymerization activity have been disclosed. In such a supported solid catalyst component, it is desirable to control the shape of particles of the solid catalyst component, and some methods are known. On the other hand, as a process for polymerizing olefins,
In recent years, a gas phase polymerization process, which is safer, resource-saving and energy-saving process, has been adopted as compared with a slurry polymerization process using a conventional polymerization solvent. However, as a solid catalyst component suitable for gas phase polymerization of olefins, it is possible to obtain an olefin polymer having a relatively large particle size and a spherical shape, excellent crush resistance during polymerization, and high stereoregularity. Is often insufficient. Particularly, if the crush resistance is not sufficient, the amount of fine powder of olefin polymer particles obtained increases, and the problem that fine powder polymer adheres to the wall of the polymerization vessel,
This causes operational problems such as deterioration of powder flow characteristics and difficulty in discharging the olefin polymer from the polymerization vessel.

As one of the prior art, it is obtained by emulsifying a melt of a carrier component in a suitable oil to form spherical molten particles, which are then added to a cooled hydrocarbon medium and rapidly solidified. Method using the prepared carrier (JP-A-55-135)
102, JP-A-55-135103, JP-A-56-67311). Although this method can obtain a solid catalyst component having an improved shape to a certain extent, it is not sufficient because it is difficult to obtain a spherical catalyst having a large particle size as a catalyst component for gas phase polymerization of olefins.

Another method is disclosed in JP-A-49-65999.
JP-A-52-38590, JP-A-58-58
45206, JP-A-57-198709,
JP-A-59-131606, JP-A-63-289
Japanese Patent Publication No. 005 discloses a method of using a carrier obtained by spraying a water or alcohol solution of a magnesium compound in a heated nitrogen stream and evaporating water or alcohol from the generated droplets by heated nitrogen. Further, in Japanese Patent Publication No. 63-503550, a mixture of magnesium chloride, alcohol and an electron donor is sprayed in a molten state into a chamber cooled with an inert liquid fluid, and the carrier obtained without evaporation of the solvent is used. The method used is shown. The carrier by the above-mentioned spray method has a relatively large particle size, but when the titanium halide treatment is subsequently carried out, the carrier is broken and fine particles are generated, and the solid catalyst for olefin polymerization obtained by using the carrier. The ingredients are
There was a problem that they were insufficient in terms of spheroidization, crush resistance during polymerization, and polymerization activity.

On the other hand, the applicant of the present invention previously disclosed in Japanese Patent Laid-Open No. 3-1190
No. 03 (hereinafter sometimes referred to as the previous invention), a mixture of a magnesium compound and an alcohol is sprayed in a molten state to obtain a spherical solid component without substantial evaporation of the alcohol, and then the alcohol is removed from the solid component. Is partially removed to obtain a spherical carrier, and then the carrier is contacted with a halogen-containing titanium compound and an electron donor to obtain a final solid catalyst component for olefin polymerization. According to this method, a spherical and large particle size solid catalyst component for olefin polymerization can be obtained. However, when used for gas phase polymerization of an olefin, further improvement is desired in terms of crush resistance during polymerization. It was

[0006]

As described above, the solid catalyst component for olefin polymerization obtained by the method of the prior art is used as an olefin polymerization catalyst in combination with an organoaluminum compound and, if necessary, an electron donor. In this case, it has a good shape, a relatively large particle size, excellent crush resistance during polymerization, and the ability to obtain an olefin polymer having high stereoregularity with high polymerization activity. Was insufficient as a solid catalyst component for gas phase polymerization of olefin, which was desired.

The inventors of the present invention have earnestly studied to solve the above problems of the prior art and to invent a catalyst for olefin polymerization suitable for gas phase (co) polymerization of olefins and a method for producing an olefin polymer. As a result, the above invention was improved, and a molten mixture of a magnesium compound represented by a specific compositional formula and an alcohol was sprayed in a cooled spray tower to obtain a solid component without substantial evaporation of the alcohol, A solid obtained by removing a specific amount of alcohol from the solid component under the conditions described in 1. above, using the solid component having a specific X-ray diffraction spectrum as a carrier, and contacting the carrier with a halogen-containing titanium compound and an electron donor. When using as a solid catalyst component for olefin polymerization, it has been found to solve the problems of the prior art,
The present invention has been completed based on this finding.

As is apparent from the above description, the object of the present invention is that it is suitable for vapor phase polymerization of olefins, has a good shape, has a relatively large particle size, and is excellent in crush resistance during polymerization. And a catalyst for olefin (co) polymerization, in which an olefin polymer having high stereoregularity can be obtained with high polymerization activity, a solid catalyst component for olefin polymerization, an organoaluminum compound, and, if necessary, an electron donor are combined ,
Another object of the present invention is to provide a method for producing an olefin polymer, which comprises (co) polymerizing an olefin in the presence of the catalyst.

[0009]

The present invention provides the following (1).
Or (4). (1) a) A mixture (A) of a magnesium compound and an alcohol is sprayed in a molten state into a spray tower, and the inside of the spray tower is cooled to a temperature at which a solid component (B) is obtained without substantial evaporation of alcohol. To obtain the solid component (B), the alcohol is partially removed from the solid component (B) to obtain the solid component (C), and then the solid titanium component (D) is added to the solid component (C). ) And an electron donor (E1) are brought into contact with each other to obtain a solid catalyst component (F)
The composition formulas of the solid catalyst component (F) and the mixture (A) and the solid component (B) obtained by satisfying all of the following three or more manufacturing conditions are MgC:
l ₂ mROH (wherein R represents an alkyl group having 1 to 10 carbon atoms and m = 3.0 to 6.0), and the composition formula of the solid component (C) is MgCl ₂ nROH
(However, R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. In the X-ray diffraction spectrum of the solid component (C), the diffraction angle is 2
No new peak is generated at θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is determined by the diffraction angle 2θ of the X-ray diffraction spectrum of the solid component (C) 2θ = 8.5 to 9 degrees. Is less than or equal to the intensity of the maximum peak present in b), b) an organoaluminum compound (AL), and optionally c) an olefin (co) polymerization catalyst comprising an electron donor (E2). (2) The average particle size of the solid catalyst component (F) is 10 to 300 μm.
The catalyst according to 1 above which is m. (3) a) A mixture of magnesium compound and alcohol (A) is sprayed in a molten state into a spray tower, whereupon the spray tower is cooled to a temperature at which a solid component (B) can be obtained without substantial evaporation of alcohol. To obtain the solid component (B), the alcohol is partially removed from the solid component (B) to obtain the solid component (C), and then the solid titanium component (D) is added to the solid component (C). ) And an electron donor (E1) are brought into contact with each other to obtain a solid catalyst component (F)
The composition formulas of the solid catalyst component (F) and the mixture (A) and the solid component (B) obtained by satisfying all of the following three or more manufacturing conditions are MgC:
l ₂ mROH (wherein R represents an alkyl group having 1 to 10 carbon atoms and m = 3.0 to 6.0), and the composition formula of the solid component (C) is MgCl ₂ nROH
(However, R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. In the X-ray diffraction spectrum of the solid component (C), the diffraction angle is 2
No new peak is generated at θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is determined by the diffraction angle 2θ of the X-ray diffraction spectrum of the solid component (C) 2θ = 8.5 to 9 degrees. In the presence of a catalyst consisting of b) an organoaluminum compound (AL), and optionally c) an electron donor (E2), in the presence of a catalyst containing at least one of the olefins (co).
A method for producing an olefin (co) polymer, which comprises polymerizing. (4) The average particle size of the solid catalyst component (F) is 10 to 300 μ.
4. The method according to the above item 3, which is m.

The structure of the present invention will be described in detail below. The magnesium compound used in the present invention is anhydrous magnesium chloride, and may contain a trace amount of water contained in a commercial product. The alcohol used is an alcohol represented by the general formula ROH (R represents an alkyl group having 1 to 10 carbon atoms). Specifically, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 2
-Methyl-2-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 1-octanol , 2-octanol, 1-nonanol, 1-decanol and the like. Of these, ethanol is the most preferable. It is also possible to use a mixture of two or more of these alcohols.

In the production of the solid catalyst component (F) according to the present invention, first, the mixture (A) of magnesium chloride and alcohol is brought into a molten state. The mixing ratio of magnesium chloride and alcohol is the composition formula MgCl ₂ · mROH (however,
R represents an alkyl group having 1 to 10 carbon atoms. ) In m
Is mixed so as to be 3.0 to 6.0. A more preferable range of m is 3.0 to 5.8, and a particularly preferable range of m is 3.0 to 5.5. If m is less than 3.0, problems such as deterioration of the shape of the obtained solid catalyst component (F) and reduction of olefin polymerization activity occur. Further, the solid catalyst component (F) obtained when m exceeds 6.0
Shatter resistance deteriorates.

The mixture (A) of magnesium chloride and alcohol having the above composition is brought into a molten state by heating.
The heating temperature is not particularly limited as long as it is a temperature at which the mixture becomes a molten state or more, but is preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 110 to 160.
° C. If the heating temperature is too low, problems such as deterioration of the shape of the obtained solid catalyst component (F) and reduction of olefin polymerization activity occur. Further, if the heating temperature is too high, the crush resistance of the obtained solid catalyst component (F) deteriorates.

The thus obtained mixture of magnesium compound and alcohol in a molten state is fed to a spray nozzle attached to the spray tower by using a pump or a heated pressurized inert gas, and the spray tower cooled from the nozzle. Is sprayed inside. As the inert gas, an inert gas such as nitrogen, helium or argon is used, but nitrogen is most preferably used. Further, the spray nozzle has a function of dispersing a mixture of a magnesium compound and an alcohol in a molten state in the spray tower, but a two-fluid nozzle of a type for feeding an inert gas into the spray tower is preferably used. In the spray, the size of the solid component (B) to be produced or the particle size distribution is adjusted by selecting the nozzle size, the flow rate of the inert gas, or the spray flow rate of the mixture of the molten magnesium compound and alcohol. It is possible to

The spray for producing the solid catalyst component (F) of the present invention is carried out in a cooled spray tower, and the cooling is usually a cooled inert gas or a cooled inert liquid. It is carried out by introducing a fluid such as liquid nitrogen into a spray tower. Further, during the spraying, a cooled inert hydrocarbon solvent (S1) such as hexane can be sprayed from another nozzle to accelerate the cooling. The cooling must be performed to a temperature at which the solid component (B) can be obtained without substantial evaporation of the alcohol, that is, a temperature at which the composition formula of the mixture (A) of magnesium chloride and alcohol and the solid component (B) does not change. There is. Therefore, the inside of the spray tower is usually -70 to 10 ° C, preferably -50 to
The temperature is 0 ° C, particularly preferably -40 to -5 ° C. If the cooling temperature is too high, evaporation of alcohol will occur,
The particle shape of the obtained solid component (B) is poor, and moreover, it becomes inhomogeneous, so that the object of the present invention cannot be achieved. Moreover, it is not practical that the cooling temperature is too low.

After spraying by the above method, the obtained solid component (B) is collected in the inert hydrocarbon solvent (S1) introduced at the bottom of the spray tower or at the bottom of the spray tower. Examples of the inert hydrocarbon solvent (S1) used as needed during spraying include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, 1,2
-Halogenated aliphatic hydrocarbons such as dichloroethane and 1,1,2-trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene are used. Is
Aliphatic hydrocarbons are preferable, and hexane is particularly preferable. The composition of the solid component (B) has the same composition as the mixture (A) of magnesium chloride and alcohol and the mixture (A) in a molten state before spraying, and its average particle size is about 10 to 300 μm. , A spherical shape is obtained.

One embodiment of the production apparatus used for producing the solid component (B) according to the present invention is shown in FIG. 1 for explaining the present invention. In FIG. 1, a magnesium compound and alcohol are introduced into a melting tank 4 equipped with a heating jacket 5 from pipes 1 and 2, and a mixture (A) of a magnesium compound and alcohol is heated by the heating jacket 5 to be in a molten state. The molten mixture (A) is introduced from the pipe 7 into the spray tower 9 cooled by the cooling jacket 10 from the two-fluid nozzle 8 by the pressurized nitrogen introduced from the pipe 3 through the heat retaining pipe 6. It is sprayed with heated nitrogen. Further, an inert hydrocarbon solvent (S1) 11 is previously introduced into the lower part of the spray tower and cooled. The solid component (B) produced by cooling and solidifying the molten mixture (A) in the spray tower 9 is collected in the inert hydrocarbon solvent (S1) 11 at the lower part of the spray tower. The solid component (B) thus obtained is an inert hydrocarbon solvent (S1).
Along with this, it is taken out from the pipe 12 and, if necessary, the inert hydrocarbon solvent (S1) is separated, and then sent to the next step.
On the other hand, a gas component and a solid component (B) entrained in the gas
Is introduced into the cyclone 14 via the pipe 13. The entrained solid component (B) is discharged from the pipe 15, and the gas component is discharged from the pipe 16.

In the production of the solid catalyst component (F) according to the present invention, following the above steps, the alcohol is partially removed from the obtained solid component (B) to obtain the solid component (C). As a method for partially removing alcohol, various known methods can be used. For example, a method of heating the solid component (B), a method of placing the solid component (B) under reduced pressure, and a method of ventilating the solid component (B) with an inert gas heated at atmospheric temperature or heated are mentioned. Furthermore, it is also possible to use these partial removal methods of alcohol in combination. Among these methods, as a method that can easily achieve the object of the present invention, a method in which and are combined is preferably cited.

Alcohol is partially removed from the solid component (B) by the above process, and the composition of the solid component (C) after the alcohol partial removal process is represented by the formula MgCl ₂ · n.
In ROH (provided that R represents an alkyl group having 1 to 10 carbon atoms), it is necessary to select conditions for the step of removing the alcohol portion so that n falls within the range of 0.4 to 2.8. A more preferable range of n is 0.8 to 2.5, and a particularly preferable range of n is 1.0 to 2.2. n
Is less than 0.4, the olefin polymerization activity of the obtained solid catalyst component for olefin polymerization is lowered. Further, when n exceeds 2.8, the solid component (C) is destroyed in the subsequent contact step with titanium halide, and the obtained solid catalyst component (F) contains amorphous fine powder particles. The crush resistance deteriorates.

In the production of the solid catalyst component (F) according to the present invention, if the solid component (C) only satisfies the above conditions, it is not sufficient to achieve the object of the present invention.
Furthermore, in the X-ray diffraction spectrum of the solid component (C),
Compared with the X-ray diffraction spectrum of the solid component (B), no new peak is generated at the diffraction angle 2θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is the solid component (C). ) X-ray diffraction spectrum diffraction angle 2θ = 8.5-9
It must be less than or equal to the intensity of the maximum peak that is present every second. At the diffraction angle 2θ = 7 to 8 degrees, the diffraction angle 2θ = 8.5
If a new large peak exceeding the intensity of the peak existing at -9 degrees occurs, the crush resistance of the obtained solid catalyst component (F) deteriorates.

In addition to the above-mentioned conditions, the conditions for the above-mentioned alcohol partial removal step satisfying the above X-ray diffraction spectrum conditions are: It should be noted that it is preferable to carry out the above step, and the alcohol removing step also takes a relatively long time. As specific conditions, for example, a container equipped with a vibrating device in which the solid components (B) to (C) flow is used, and the heating temperature is 0 under reduced pressure.
The partial alcohol removal step is carried out under conditions of -100 ° C, preferably 10-80 ° C, and most preferably 20-55 ° C for 2-1000 hours, preferably 3-500 hours.

In the method of the present invention, the halogen-containing titanium compound (D) and the electron donor (E1) are brought into contact with the solid component (C) obtained by the above-mentioned method to obtain the final solid catalyst component for olefin polymerization. A solid component (F) is obtained.

The halogen-containing titanium compound (D) to be brought into contact with the solid component (C) has a general formula of Ti (OR ¹ )
_4-u X _u (In the formula, R ¹ represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen.
Is an arbitrary number of 0 <u ≦ 4. ) A halogen-containing titanium compound represented by Specifically, titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, butoxytitanium tribromide. , Diethoxytitanium dichloride,
Examples thereof include dibutoxy titanium dichloride, diethoxy titanium dibromide, dibutoxy titanium dibromide, and triethoxy titanium chloride. One or more of these halogen-containing titanium compounds (D) are used. Most preferred is titanium tetrachloride.

The electron donor (E1) to be brought into contact with the solid component (C) is any one of oxygen, nitrogen, sulfur and phosphorus.
An organic compound having the above atoms is used. Among them, electron donors such as ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, isocyanates, phosphines, phosphites, phosphinites, acid anhydrides, and organosilicon compounds having a Si—O—C bond. Is used. Of these electron donors, esters are preferably used. Specifically, aliphatic monocarboxylic acid esters such as ethyl acetate, vinyl acetate, isobutyl acetate, octyl acetate, cyclohexyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid. Aromatic monocarboxylic acid esters such as cyclohexyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl methyl malonate, ethyl malonate Diethyl acid butyl, diethyl butyl malonate, dibutyl maleate, dioctyl maleate, diethyl butyl maleate, diethyl itaconate, etc., aliphatic polycarboxylic acid esters, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-phthalate n- Propyl, diisopropyl phthalate, di -n- butyl, diisobutyl phthalate, di -n- heptyl phthalate, di-2-ethylhexyl phthalate, di -n
-Aromatic polycarboxylic acid esters such as octyl, diethyl isophthalate, diethyl terephthalate, and dibutyl naphthalene dicarboxylate. One or more of these electron donors (D) are used. Most preferred are aromatic polycarboxylic acid esters.

When the solid component (C) is brought into contact with the halogen-containing titanium compound (D) and the electron donor (E1), the solvent (S2) is not used if the contact treatment conditions are selected. As a matter of course, the solid component (C) contains a halogen-containing titanium compound (D) and an electron donor (E1).
It is preferable to use the solvent (S2) from the viewpoint of controlling the reaction when contacting with each other and preventing deterioration of the particle shape of the final solid catalyst component (F), generation of fine particles, and deterioration of crush resistance. Is a desirable embodiment of. As the solvent (S2) that can be used, the same inert hydrocarbon solvent as that described as the inert hydrocarbon solvent (S1) that is optionally used in the spraying step described above is used.

The amounts of the solid component (C), the halogen-containing titanium compound (D), the electron donor (E1) and the solvent (S2) used are shown below. Mg in solid component (C)
Halogen-containing titanium compound (D) per mol of Cl ₂
Is used in an amount of 1 to 100 mol, preferably 3 to 50 mol.
The electron donor (E1) is MgCl ₂ 1 in the solid component (C).
0.01 to 1.0 mol, preferably 0.0
1 to 0.8 mol is used. The solvent (S2) is 0～100Dm ³ relative to the solid component (C) 1 kg, preferably 5～70Dm ³ used.

The order of contacting the halogen-containing titanium compound (D) and the electron donor (E1) to the solid component (C) is not particularly limited, but the solid component (C) is suspended in the solvent (S2). After that, a method of first contacting the halogen-containing titanium compound (D) and then contacting the electron donor (E1) is preferable. Further, a method of further contacting the halogen-containing titanium compound (D) after the contact with the electron donor (E1) is also a preferred embodiment of the present invention.

As the conditions for contacting the halogen-containing titanium compound (D) and the electron donor (E1) with the solid component (C), the contact temperature is −20 to 200 ° C., preferably 0 to 200 ° C., most preferably Is 30 to 150 ° C.,
Contact time is 5 minutes to 20 hours, preferably 10 minutes to 1
5 hours, most preferably 10 minutes to 10 hours.

After the contact of the halogen-containing titanium compound (D) and the electron donor (E1) with the solid component (C),
The solid according to the present invention is obtained by separating the solid obtained by a method such as filtration or decantation, and subsequently washing the separated solid with an inert hydrocarbon solvent (S3) to remove unreacted substances or by-products. A catalyst component (F) is obtained. As the inert hydrocarbon solvent (S3) used for washing, the same inert hydrocarbon solvent as the above-mentioned inert hydrocarbon solvent (S1) or solvent (S2) can be used.

The average particle size of the solid catalyst component (F) thus obtained depends on the average particle size of the solid component (C),
In the subsequent process, the particle size will be reduced to some extent, but normally,
The average particle diameter of 90 to 100% of the average particle diameter of the solid component (C) is shown. Here, the average particle size of the solid catalyst component (F) preferable for achieving the object of the present invention is 10 to 300 μm.
m, more preferably 15 to 200 μm.

The solid catalyst component (F) obtained by the above-mentioned method is combined with an organoaluminum compound (AL) and, if necessary, an electron donor (E2) in the same manner as a known solid catalyst component for olefin polymerization. As a catalyst, it is used for olefin polymerization, or more preferably, it is used for olefin polymerization as a catalyst that is preactivated by reacting a small amount of olefin with the catalyst.

The organoaluminum compound (AL) used for the polymerization of olefins has a general formula of AlR ² _p R ³ _q
X _{3- (p + q)} (wherein R ² and R ³ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p and q are 0 <p + q
Represents an arbitrary number of ≦ 3. The organic aluminum compound represented by the formula (1) is used.

Specific examples thereof include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum, tri-n-octylaluminum and the like. Alkyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and other dialkyl aluminum monohalides, diethyl aluminum hydride and other dialkyl aluminum hydrides, ethyl aluminum sesquichloride and other alkyl aluminums Sesquihalide, ethyl aluminum dichlora Include monoalkyl aluminum dihalides such as soil, it may also be used alkoxyalkyl aluminum such as other diethoxy monoethyl aluminum. Of these, preferred are trialkylaluminums and dialkylaluminum monohalides, and most preferred are trialkylaluminums. Further, these organoaluminum compounds can be used not only as one type but also as a mixture of two or more types.

As the electron donor (E2), a known electron donor which is optionally used for the purpose of controlling the stereoregularity of the olefin polymer obtained during ordinary olefin polymerization is used. Specifically, the same electron donors as those mentioned as the above-mentioned electron donor (E1) are used, and the compound having a Si—O—C bond is particularly preferable. Specifically, methyltrimethoxysilane, methyltriethoxysilane, t-butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyl. Ethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-
Examples thereof include butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, trimethyltriethoxysilane and the like. These electron donors may be used alone or in combination of two or more.

The amount of each catalyst component used is the same as in the case of using a known catalyst component for olefin polymerization. Specifically, 1 mol of Ti atom in the solid catalyst component obtained by the method of the present invention is replaced by A in the organoaluminum compound (AL).
The organoaluminum compound (AL) is used so that 1 atom is 1 to 2000 mol, preferably 5 to 1000 mol, and the electron donor (E2) is 0 to 1 mol of Al atom in the organoaluminum compound (AL). It is used in an amount of -10 mol, preferably 0.01-5 mol.

As the olefin used for pre-activation, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene are used. -1, 2
And branched-chain monoolefins such as methylpentene-1. These olefins may be the same as or different from the olefin to be polymerized, and two or more kinds of olefins may be mixed and used.

A catalyst in which a solid catalyst component for olefin polymerization by the method of the present invention, an organoaluminum compound (AL), and, if necessary, an electron donor (E2) are combined, or a small amount of olefin is reacted with the catalyst to carry out preliminary activity. The olefin polymerization method using the converted catalyst is not limited,
It is also suitable for liquid phase polymerization such as suspension polymerization or bulk polymerization carried out in a solvent, but when it is used for gas phase polymerization, the advantages of the solid catalyst component for olefin polymerization by the method of the present invention are particularly exerted. Further, in the polymerization of the olefin, it is preferable to use a preactivated catalyst.

Pre-activation is carried out in the presence of a catalyst in which the above-mentioned catalyst components are combined with 0.05 g of olefin per 1 g of the solid catalyst component obtained by the method of the present invention.
Using 5,000 g, preferably 0.05 g to 3,000 g, olefin is reacted at 0 ° C. to 100 ° C. for 1 minute to 20 hours, and 0.01 g to 2,000 per 1 g of the solid catalyst component.
It is desirable to produce 0 g, preferably 0.05 to 500 g of olefin polymer.

The catalyst thus obtained or the preactivated catalyst is used for the polymerization of olefins. As olefin polymerization conditions, the polymerization temperature is 20 to 150 ° C., the polymerization pressure is 0.1 to 5 MPa, and the polymerization is usually performed for about 5 minutes to 20 hours. During the polymerization, addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as in the conventional polymerization method.

The olefins used for the polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 3-methylbutene-1,
Not only branched chain monoolefins such as 4-methylpentene-1 and 2-methylpentene-1, but also butadiene, isoprene, chloroprene, 1,4-hexadiene, 1,7-
Octadiene, 1,9-decadiene, 4-methyl-1,
Examples thereof include diolefins such as 4-hexadiene, 5-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene, allyltrimethylsilane, and styrene. In particular, when an olefin having 3 or more carbon atoms which may contain silicon is polymerized, a highly stereoregular olefin polymer is obtained. Further, these olefins are not only homopolymerized with each other, but are also mutually combined with other olefins, for example, propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or the like.
Copolymerization can be performed by combining three components such as propylene, ethylene, and butene-1, and further, block copolymerization can be performed by changing the kind of olefin fed in multistage polymerization.

[0040]

The present invention will now be described in more detail with reference to Examples.
Will be described. In addition, used in Examples and Comparative Examples
The definitions and measurement methods of the existing terms are as follows. (1) X-ray diffraction spectrum: X-ray source is Cu-Kα ray
X-ray diffractometer JDX8200T manufactured by JEOL Ltd.
The tube voltage was 50 KV and the tube current was 150 mA. (2) Particle size distribution of solid components: Malvern Instruments
Particle size distribution measuring device (laser
Starsizer MS20) is used to convert solid components to minerals.
Disperse in oil and measure the particle size distribution of the solid component
Was. (3) Average particle size: The particle size distribution was measured according to (2) above.
The volume of the solid component for each particle size is added up, and the added volume is
The particle size at 50% is shown. (Unit: μm) (4) Span: Similar to (3) above, the total volume is 9
The particle size at 0% is D_0.9Similarly, the total volume is 10% of the total.
Particle size at time D_0.1 , The average grain size of (3) above is D _0.5 And table
If the following formula, span = (D_0.9 -D_0.1 ) / D_0.5 
Defined by It is an index showing the degree of particle size distribution, and span
Is large, the particle size distribution is wide, and if the span is small, the particle size distribution is
Indicates that is narrow. (5) Polymerization activity: 1 kg of solid catalyst component for olefin polymerization
Shows the amount of polymerized olefin (kg) per unit
It is a measure of total activity. (Unit: kg ・ Polymer / kg ・
Solid catalyst component) (6) BD: shows bulk density (unit: kg / m)^Three )

Example 1 (1) Production of solid component (B) A solid component (B) was produced using the apparatus shown in FIG. Stainless steel melting tank 4 with an internal volume of 60 dm ³ purged with nitrogen
Then, 8 kg of anhydrous MgCl ₂ was introduced from the pipe 1 and 15.5 kg of dry ethanol was introduced from the pipe 2. The composition (A) was heated to 130 ° C. by passing heated steam through the jacket 5 with stirring, and the composition was MgC.
A mixture (A) in the molten state having l ₂ · 4.0 EtOH was obtained. After further stirring for 2 hours, nitrogen heated to 130 ° C. was introduced into the melting tank 4 through the pipe 3, and the pressure of the gas phase portion of the melting tank 4 was increased to 0.5 MPa. Subsequently, the uniform molten mixture (A) was passed through the pipe 6 at a rate of 15 kg / h, and then the two-fluid nozzle 8 introduced the cooled spray tower 9 into the pipe 7.
Sprayed with heated nitrogen of 130 ° C. 250 dm ^{3 of} n-hexane cooled to −15 ° C. was previously introduced into the spray tower 9, and a refrigerant of −30 ° C. was used to maintain this temperature during spraying and to cool the inside of the spray tower 9. Was poured into a jacket 10 attached to the spray tower 9. The nozzle 8 is a small precision two-fluid nozzle (BN-90, manufactured by Shizuto Kyoritsu Shokai), and the pipe 7
The flow rate of the heated nitrogen introduced from was 40 dm ³ / min. The solid component (B) produced by cooling and solidifying the molten mixture (A) is cooled n introduced into the bottom of the spray tower 9.
-Collected in hexane 11. Solid component (B) and n-
After taking hexane out of the system through the pipe 12, n-hexane was separated to obtain 18.8 kg of a solid component (B).
From the obtained analysis result of the solid component (B), the composition of this solid component (B) is the same as that of the molten mixture (A) MgCl ₂ ·.
It was 4.0 EtOH. The shape was spherical, the average particle size was 130 μm, and the span was 1.5.

(2) Production of solid catalyst component (F) In order to partially remove ethanol in 18.8 kg of the obtained solid component (B), the solid component was transferred to a vacuum dryer having an internal volume of 450 dm ^{3 and} a vacuum of 267 Pa was applied. 20 ° C at 35 ° C
After further drying for 4 hours at 45 ° C. and then for 24 hours at 50 ° C., 11.5 kg of solid component (C) was obtained. From the analysis result, the composition of this solid component (C) is MgCl ₂ · 1.7.
It was EtOH. With respect to the solid component (C), small particles smaller than 65 μm and particles larger than 180 μm were removed using a sieve to obtain 8.6 kg of the solid component (C) having an average particle diameter of 120 μm and a span of 0.9.

Solid component (B) (M
The X-ray diffraction spectrum of (gCl ₂ · 4.0 EtOH) is shown in FIG. 2. An X-ray diffraction spectrum of the solid component (C) (MgCl ₂ · 1.7EtOH) from which ethanol was partially removed is shown in FIG. 3. No new peak appeared at the diffraction angle 2θ = 7 to 8 degrees.

A stainless reactor having an internal volume of 110 dm ³ equipped with a condenser and a filter was charged with 8.6 kg of a solid component (C), 37 dm ^{3 of} toluene, and 74 kg of titanium tetrachloride as a halogen-containing titanium compound (D). The mixture in the reactor was heated with stirring, and when it reached 100 ° C., 1.8 kg of diisobutyl phthalate was added as an electron donor (E1). Further, the inside of the reactor was heated to 120 ° C., and contact treatment was carried out at the same temperature for 1.5 hours. After the lapse of processing time, the liquid phase part was removed by filtration. Next, toluene 37d
After adding m ³ and 74 kg of titanium tetrachloride and heating at 120 ° C. for 1 hour, the liquid phase part was removed by filtration. Then, after adding 70 dm ³ of toluene and heating at 115 ° C. for 0.5 hour, the liquid phase part was removed, and n-hexane was added at 50 times per time.
Using dm ^{3 and} washing three times, 6.0 kg of the final solid catalyst component (F) for olefin polymerization was obtained. The obtained solid catalyst component (F) was spherical, the average particle size was 115 μm, and the span was 1.0. The titanium content of the solid catalyst component (F) was 2.0% by weight.

(3) Production of olefin polymer After replacing a stainless steel reactor having an internal capacity of 1.5 dm ³ equipped with a stirrer with an inclined blade with nitrogen, the reactor was used as a saturated hydrocarbon solvent by Esso Oil Co., Ltd. Made of CRYSTOL
-52 to 0.83 dm ³ , triethylaluminum 1
0.5 mmol, diisopropyldimethoxysilane 1.
After 6 mmol and 14 g of the solid catalyst component (F) obtained in (2) above were added at room temperature, the mixture was heated to 40 ° C. and then reacted at a propylene partial pressure of 0.05 MPa for 7 hours to obtain a preactivated catalyst. (Propylene 3.0 g reaction per 1 g of solid catalyst component (F))

In a horizontal gas phase polymerizer (length / diameter = 3) equipped with a stirrer with an internal volume of ³ dm ³ which was replaced with nitrogen, 500 μ was added.
100 g of polypropylene powder (average particle size 1500 μm) from which polymer particles of m or less are removed is introduced, and 16.8 m of the above-mentioned pre-activated catalyst as a solid catalyst component (F).
g, triethylaluminum 1.4 mmol, and diisopropyldimethoxysilane 0.14 mmol are added, and then hydrogen 76 mmol is introduced, and then propylene gas is introduced to 70 ° C., and the polymerization reactor internal pressure is 2.15 MPa for 2 hours, Gas phase polymerization of propylene was performed (first polymerization). After polymerization, polypropylene particles will be 3 in the polymerization vessel.
After extracting the polymer so that 0 g remained, the same amount of each catalyst component as in the first polymerization was introduced, and the same polymerization as in the first polymerization was repeated (second polymerization). 4 such operations
Repeated 3 times (third polymerization to sixth polymerization). The polymerization activity in the sixth polymerization was 16500 kg-polymer / kg-
It was a solid component (F) and had a BD of 420 kg / m ³ . The polymer obtained was spherical and had an average particle size of 2300 μm.
And the fine powder polymer of 210 μm or less is 0.01% by weight.
Met.

Comparative Example 1 (1) Manufacture of solid component (B) Solid component (B) 18.8 in the same manner as in Example 1 (1).
kg.

(2) Production of solid catalyst component The conditions for partially removing ethanol in 18.8 kg of the obtained solid component (B) are as follows: a reduced pressure of 267 Pa, 60 ° C. for 2 hours, and 70 ° C. 3.5 at 80 ° C for 3 hours
The same procedure as in (2) of Example 1 was repeated except that the time was changed to obtain 11.5 kg of a solid component. With respect to the solid component, small particles smaller than 65 μm and particles larger than 180 μm were removed using a sieve to obtain 6.9 kg of a solid component having an average particle diameter of 115 μm and a span of 1.2. Subsequently, the above (1), drying under reduced pressure and sieving were separately repeated in the same manner to obtain 13.8 kg of solid components.

The composition of the above solid component, from which ethanol was partially removed, was MgCl ₂ .1.7 EtOH. The X-ray diffraction spectrum of the solid component is shown in FIG. A new peak appeared at the diffraction angle 2θ = 7.6 degrees, and the intensity of the new peak was higher than the intensity of the peak at the diffraction angle 2θ = 8.8 degrees.

In the same manner as in (2) of Example 1, except that 8.6 kg of the solid component after sieving obtained by the above method was used in place of the solid component (C), the final solid catalyst component was obtained. Was obtained in an amount of 6.0 kg. The final solid catalyst component obtained had an average particle size of 75 μm and a span of 1.6.

(3) Production of olefin polymer Preliminary activity was carried out in the same manner except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F) in (3) of Example 1. A chemical catalyst was obtained. Using the obtained pre-activated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1 to obtain a polymer.

Comparative Example 2 (1) Production of Solid Component (B) Solid component (B) 18.8 in the same manner as in Example 1 (1).
kg.

(2) Production of solid catalyst component In (2) of Example 1, the solid component (C) was replaced with the solid component (B) obtained in the above (1) without drying under reduced pressure, and a sieve was used. Average particle size of 120μ obtained by removing small particles smaller than 65 μm and particles larger than 180 μm.
8 out of 14.9 kg of solid component having m and span of 1.0.
4.1 kg of the final solid catalyst component was obtained in the same manner except that 6 kg was used. The final solid catalyst component obtained was crushed and had an average particle size of 52 μm and a span of 1.8.

(3) Production of olefin polymer Preliminarily prepared in the same manner as in (3) of Example 1 except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). An activated catalyst was obtained. Using the obtained pre-activated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1 to obtain a polymer.

Comparative Example 3 (1) 8 kg of anhydrous MgCl ₂ and dry ethanol 6.6
Spraying was performed in the same manner as in (1) of Example 1 except that 1 kg of a solid component was obtained. From the analysis result of the solid component, the composition of this solid component was the same as that of the raw material anhydrous magnesium chloride and ethanol mixture, MgCl ₂ ·.
It was 1.7 EtOH. In addition, the obtained solid component contains a lot of aggregates and irregular ones, and has an average particle size of 1
It had a wide particle size distribution of 80 μm and a span of 2.1.

(2) Solid component 12.3 obtained in (1) above
3. Small particles smaller than 65 μm and particles larger than 180 μm were removed using a sieve without drying under reduced pressure to obtain a solid component having an average particle size of 119 μm and a span of 1.1.
9 kg were obtained. Subsequently, the above (1) and sieving were separately repeated in the same manner to obtain 9.8 kg of solid components together.

The final solid catalyst component was obtained in the same manner as in Example 1 (2) except that 8.6 kg of the solid component after sieving obtained by the above method was used in place of the solid component (C). 6.6 kg was obtained. The final solid catalyst component obtained had an average particle size of 118 μm and a span of 1.1.

(3) A preactivated catalyst was obtained in the same manner as in (3) of Example 1 except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). It was (3) of Example 1 using the obtained pre-activated catalyst
Gas phase polymerization of propylene was carried out in the same manner as above to obtain a polymer.

Comparative Example 4 (1) 8 kg of anhydrous MgCl ₂ and dry ethanol 25.
Spraying was performed in the same manner as in (1) of Example 1 except that 2 kg was used to obtain 26.5 kg of a solid component. From the analysis result of the solid component, the composition of this solid component was MgCl 2 having the same composition as the raw material anhydrous magnesium chloride and ethanol mixture.
A ₂ · 6.5EtOH, the average particle size is 125 [mu] m,
The span was 1.4.

(2) Solid component 2 obtained in (1) above
Transferred to a vacuum dryer for partial removal of ethanol in 6.5 kg and dried continuously under reduced pressure of 267 Pa at 35 ° C. for 22 hours, 45 ° C. for 6 hours, 53 ° C. for 20 hours to solidify. 10.6 kg was obtained. From the analysis result, the composition of this solid was MgCl ₂ · 1.7 EtOH. The resulting solid was subsequently screened to remove small particles below 65 μm and particles above 180 μm,
8.9 kg of a solid having an average particle size of 120 μm and a span of 1.0 was obtained.

In Example 1 (2), the solid component (C) was replaced by the above-mentioned solid obtained by the above-mentioned method 8.9.
In the same way, except using 8.6 kg out of kg,
6.1 kg of the final solid catalyst component was obtained. The final solid catalyst component obtained had an average particle size of 92 μm and a span of 1.4, and crushing occurred during the contact treatment between titanium tetrachloride and diisobutyl phthalate.

(3) A preactivated catalyst was obtained in the same manner as in (3) of Example 1 except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). It was (3) of Example 1 using the obtained pre-activated catalyst
Gas phase polymerization of propylene was carried out in the same manner as above to obtain a polymer.

Comparative Example 5 (1) In the same manner as in (1) of Example 1, solid component (B) 1
8.8 kg was obtained.

(2) Obtained solid component (B) 18.8k
The conditions for partially removing ethanol in g are 267
Under reduced pressure of Pa, 35 ° C for 20 hours, 45 ° C for 4 hours, 5
The same procedure as in (2) of Example 1 was repeated except that the treatment was continuously performed at 3 ° C. for 37 hours to obtain 6.3 kg of a solid component. From the analysis results, the composition of this solid component is MgCl ₂ · 0.2 Et
It was OH. Further, with respect to the obtained solid component, small particles smaller than 65 μm and particles larger than 180 μm were removed using a sieve, and an average particle diameter of 118 μm and a span of 1.
4.5 kg of a solid component of 1 were obtained. Subsequently, the above (1), reduced pressure drying and sieving are separately repeated in the same manner,
The solid components were combined to obtain 9.0 kg.

In the same manner as in (2) of Example 1, except that 8.6 kg of the solid component after sieving obtained by the above method was used in place of the solid component (C), the final solid catalyst component was obtained. 8.4 kg was obtained. The final solid catalyst component obtained had an average particle size of 118 μm and a span of 1.1.

(3) A preactivated catalyst was obtained in the same manner as in (3) of Example 1, except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). It was (3) of Example 1 using the obtained pre-activated catalyst
Gas phase polymerization of propylene was carried out in the same manner as above to obtain a polymer.

Comparative Example 6 (1) 10 kg of anhydrous MgCl ₂ and dry ethanol 7.
Spraying was performed in the same manner as in (1) of Example 1 except that 3 kg was used to obtain 13.7 kg of a solid component. From the analysis result of the solid component, the composition of this solid component was the same as that of the mixture of magnesium chloride and ethanol before spraying MgCl ₂ ·.
It was 1.5 EtOH. The obtained solid component had an average particle size of 190 μm and a span of 2.3, and contained many aggregates and irregular shapes.

(2) Solid component 1 obtained in (1) above
In order to partially remove ethanol in 3.7 kg, the mixture was transferred to a vacuum dryer and dried under reduced pressure of 267 Pa at 55 ° C. for 7 hours to obtain 11.2 kg of a solid. From the analysis result, the composition of this solid was MgCl ₂ · 1.0 EtOH. Furthermore, small particles smaller than 65 μm and particles larger than 180 μm were removed from the obtained solid by using a sieve to obtain 4.5 kg of a solid having an average particle diameter of 122 μm and a span of 1.2.
Subsequently, the above (1), drying under reduced pressure, and sieving were separately repeated in the same manner to obtain 9.0 kg of solids.

In (2) of Example 1, the solid after the sieving obtained by the above method in place of the solid component (C) was 8.
In the same manner except that 6 kg was used, 8.4 kg of the final solid catalyst component was obtained. The final solid catalyst component obtained had an average particle size of 121 μm and a span of 1.1.

(3) A pre-activated catalyst was obtained in the same manner as in (3) of Example 1 except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). It was (3) of Example 1 using the obtained pre-activated catalyst
Gas phase polymerization of propylene was carried out in the same manner as above to obtain a polymer.

Table 1 shows the production conditions and production results of Example 1 and Comparative Examples 1 to 6 described above.

[0072]

[Table 1]

Example 2 (1) Production of solid component (B) 8 kg of anhydrous MgCl ₂ and 19.4 kg of dry ethanol
Was used, and spraying was carried out in the same manner as in (1) of Example 1 except that the heating nitrogen flow rate introduced into the two-fluid nozzle 8 from the pipe 7 was 50 dm ³ / min, and the solid component (B) .9 kg was obtained. From the analysis results of the solid component (B), the composition of this solid component was the same as that of the magnesium chloride / ethanol mixture (A) before spraying MgCl ₂ ·.
It was 5.0 EtOH. The obtained solid component (B) had an average particle size of 100 μm and a span of 1.3.

(2) Production of solid catalyst component (F) The solid component (B) obtained in the above (1) was transferred to a vacuum dryer to partially remove ethanol in 21.9 kg, and the vacuum was reduced to 267 Pa. Under 35 ° C for 22 hours, then 45
After drying at 4 ° C. for 4 hours and then at 56 ° C. for 18 hours, 11.0 kg of a solid component (C) was obtained. From the analysis result, the composition of this solid component (C) was MgCl ₂ · 1.5EtOH. With respect to the solid component (C), small particles smaller than 45 μm and particles larger than 150 μm were removed using a sieve, and the solid component (C) 8.7 having an average particle diameter of 93 μm and a span of 0.9.
kg.

X-ray diffraction analysis of the above solid component (C) (MgCl ₂ .1.5 EtOH) from which ethanol was partially removed was carried out. Although a new peak appeared at the diffraction angle 2θ = 7.6 degrees, its intensity was 1/2 of that of the peak at the diffraction angle 2θ = 8.8 degrees.

The final olefin was prepared in the same manner as in (2) of Example 1 except that 8.6 kg of the solid component (C) obtained by the above-mentioned method was used as the solid component (C). 5.9 kg of a solid catalyst component (F) which is a solid catalyst component for polymerization was obtained. The obtained solid component (F) had an average particle size of 90 μm and a span of 1.0.

(3) Production of Olefin Polymer As the solid catalyst component (F) in (3) of Example 1,
A preactivated catalyst was obtained in the same manner except that the solid catalyst component (F) obtained in (2) above was used. Using the obtained pre-activated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1 to obtain a polymer.

Comparative Example 7 (1) A solid component (B) was obtained in the same manner as in (1) of Example 2.

(2) In order to partially remove ethanol in 21.9 kg of the solid component (B) obtained in the above (1), it was transferred to a reduced pressure dryer and 35 ° C. under a reduced pressure of 267 Pa.
After drying for 2 hours, 18.5 kg of a solid component was obtained. From the analysis results, the composition of this solid component is MgCl ₂ · 4.0EtO.
H. For the solid component, small particles of less than 45 μm and 150 μm were passed through a sieve in the same manner as in (2) of Example 2.
Particles larger than m were removed to obtain 15.4 kg of a solid component having an average particle size of 95 μm and a span of 1.1.

In the same manner as in Example 2 (2), except that 8.6 kg of the solid component after sieving obtained by the above method was used in place of the solid component (C), the final solid catalyst component was obtained. Was obtained in an amount of 4.2 kg. The final solid catalyst component obtained was crushed, and had an average particle size of 52 μm and a span of 1.7.

(3) A preactivated catalyst was obtained in the same manner as in (3) of Example 2, except that the final solid catalyst component obtained in (2) above was used in place of the solid catalyst component (F). It was (3) of Example 2 using the obtained pre-activated catalyst
Gas phase polymerization of propylene was carried out in the same manner as above to obtain a polymer.

Example 3 (1) Production of solid component (B) 8 kg of anhydrous MgCl ₂ and 17.4 kg of dry ethanol
Spraying was carried out in the same manner as in (1) of Example 1 except that was used to obtain 20.5 kg of a solid component (B). From the analysis result of the solid component (B), the composition of the solid component was MgCl ₂ · 4.5 EtOH, which was the same as that of the magnesium chloride / ethanol mixture (A) before spraying. The obtained solid component (B) had an average particle diameter of 130 μm and a span of 1.5.

(2) Manufacture of solid catalyst component (F) The solid component (B) obtained in (1) above was transferred to a vacuum dryer to partially remove ethanol in 20.5 kg, and the vacuum was reduced to 267 Pa. Under 35 ° C for 19 hours, then 45
After drying at 4 ° C. for 4 hours and then at 50 ° C. for 24 hours, 13.5 kg of solid component (C) was obtained. From the analysis results, the composition of this solid component (C) was MgCl ₂ · 2.1EtOH. For the solid component (C), small particles smaller than 65 μm and particles larger than 180 μm were removed using a sieve, and the solid component (C) 1 having an average particle size of 120 μm and a span of 1.0
0.2 kg was obtained.

The solid component (C) (MgCl ₂ 2.1E)
X-ray diffraction analysis of (tOH) was performed. Diffraction angle 2θ = 7-8
No new peak appeared every time.

In (2) of Example 1, 8.6 kg of the solid component (C) obtained by the above-mentioned method, which had been sieved, was used as the solid component (C), and the electron donor (E1) was used. 5.5 kg of the solid catalyst component (F) which is the final solid catalyst component for olefin polymerization was obtained in the same manner except that 1.8 kg of di-n-butyl phthalate was used instead of diisobutyl phthalate. The resulting solid catalyst component (F) had an average particle size of 118 μm and a span of 1.0.

(3) Production of olefin polymer In the same manner as in (3) of Example 1, the solid catalyst component (F) was prepared in the same manner as above except that the solid catalyst component (F) obtained in the above (2) was used. An activated catalyst was obtained. Using the obtained pre-activated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1 to obtain a polymer.

Table 2 shows the production conditions and production results of Examples 2 to 3 and Comparative Example 7 described above.

[0088]

[Table 2]

[0089]

The main effect of the present invention is that the olefin polymerization catalyst of the present invention comprises a solid catalyst component for olefin polymerization obtained by the method of the present invention, an organoaluminum compound, and optionally an electron donor. When used for olefin polymerization, it is possible to stably produce a highly stereoregular olefin polymer for a long period of time with a remarkably high polymerization activity without causing operational problems. As is clear from Examples 1 to 3 described above, the solid catalyst component (F) obtained by the method of the present invention is excellent in crush resistance and narrow particle size distribution. In particular, when the catalyst component is used for gas phase polymerization, it is possible to obtain polymer particles having a relatively large particle size, very little generation of finely divided polymer, and high bulk density with high polymerization activity. is there.

On the other hand, when the solid catalyst component obtained by using the solid component obtained by a method other than the method of the present invention as a carrier is applied to the olefin polymerization, the generation of fine powder polymer and the low polymerization activity are observed. Therefore, it is impossible to stably produce a highly stereoregular olefin polymer (Comparative Examples 1 to 7).

[Brief description of the drawings]

1 is a solid component (B) for illustrating the method of the present invention.
3 is a process diagram of the manufacturing apparatus of FIG.

FIG. 2 shows an X-ray diffraction spectrum of the solid component (B) obtained in Example 1.

FIG. 3 shows an X-ray diffraction spectrum of the solid component (C) obtained in Example 1.

FIG. 4 shows the solid component (MgCl ₂ ·
The X-ray diffraction spectrum of 1.7 EtOH) is shown.

FIG. 5 is a manufacturing process diagram (flow sheet) of the solid catalyst component (F) for explaining the method of the present invention.

[Explanation of symbols]

 1 Raw Material Supply Pipe 2 Raw Material Supply Pipe 3 Pressurized Nitrogen Supply Pipe 4 Melting Tank 5 Heating Jacket 6 Molten Mixture (A) Transport Pipe 7 Heating Nitrogen Supply Pipe 8 Two-Fluid Nozzle 9 Spray Tower 10 Cooling Jacket 11 Inert Hydrocarbon Solvent ( S1) 12 solid component (B) acquisition pipe 13 gas exhaust pipe 14 cyclone 15 gas-entrained solid component (B) exhaust pipe 16 gas exhaust pipe

Claims (4)

[Claims] 1. A) spraying a mixture (A) of a magnesium compound and an alcohol in a molten state into a spray tower,
At this time, the solid component (B) was obtained by cooling the inside of the spray tower to a temperature at which the solid component (B) was obtained without substantial evaporation of alcohol, and then the alcohol was partially removed from the solid component (B). A solid catalyst component (F) obtained by contacting a halogen-containing titanium compound (D) and an electron donor (E1) with the solid component (C) after removing the solid component (C); The composition formulas of the solid catalyst component (F) and the mixture (A) and the solid component (B) obtained by satisfying all of the three production conditions are MgC.
l ₂ mROH (wherein R represents an alkyl group having 1 to 10 carbon atoms and m = 3.0 to 6.0), and the composition formula of the solid component (C) is MgCl ₂ nROH
(However, R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. In the X-ray diffraction spectrum of the solid component (C), the diffraction angle is 2
No new peak is generated at θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is determined by the diffraction angle 2θ of the X-ray diffraction spectrum of the solid component (C) 2θ = 8.5 to 9 degrees Is less than or equal to the intensity of the maximum peak present in b), b) an organoaluminum compound (AL), and optionally c) an olefin (co) polymerization catalyst comprising an electron donor (E2). 2. The average particle size of the solid catalyst component (F) is 10 to 10.
The catalyst according to claim 1, which is 300 μm. 3. A) spraying a mixture (A) of a magnesium compound and an alcohol in a molten state into a spray tower,
At this time, the solid component (B) was obtained by cooling the inside of the spray tower to a temperature at which the solid component (B) was obtained without substantial evaporation of alcohol, and then the alcohol was partially removed from the solid component (B). A solid catalyst component (F) obtained by contacting a halogen-containing titanium compound (D) and an electron donor (E1) with the solid component (C) after removing the solid component (C); The composition formulas of the solid catalyst component (F) and the mixture (A) and the solid component (B) obtained by satisfying all of the three production conditions are MgC.
l ₂ mROH (wherein R represents an alkyl group having 1 to 10 carbon atoms and m = 3.0 to 6.0), and the composition formula of the solid component (C) is MgCl ₂ nROH
(However, R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. In the X-ray diffraction spectrum of the solid component (C), the diffraction angle is 2
No new peak is generated at θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is determined by the diffraction angle 2θ of the X-ray diffraction spectrum of the solid component (C) 2θ = 8.5 to 9 degrees. 1 or more olefins (co) in the presence of a catalyst consisting of b) an organoaluminum compound (AL) and, if necessary, c) an electron donor (E2).
A method for producing an olefin (co) polymer, which comprises polymerizing. 4. The average particle size of the solid catalyst component (F) is 10 to 10.
The manufacturing method according to claim 3, which has a thickness of 300 μm.