JPH0820608A - Production of solid catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a catalyst excellent in crushing resistance, suitable for vapor phase polymerization of an olefin and having preferable particle diameter and shape by bringing a support obtained by partially removing an alcohol from a solid compound comprising an Mg compound and an alcohol into contact with a titanium compound and an electron donor. CONSTITUTION:This method for producing a solid catalyst component for olefin polymerization comprises partially removing an alcohol from a solid component obtained without substantial evaporation of the alcohol by spraying a melt mixture of a magnesium compound with the alcohol into a spray toward to afford a support component and bringing the support component into contact with a halogen-containing titanium compound and an electron donor. In the production of the catalyst component, a composition formula comprising the melt mixture and the solid component is expressed by MgCl/mROH [R is a 1-10C alkyl; (m) is 3-6] and a composition formula of the support component is expressed by MgCl/nROH [(n)=0.5 to 2.8] and the support component has no new peak at the diffraction angle 2theta=7 to 8 compared with X ray diffraction spectrum of the support and the solid component and even if the support component has the new peak, the strength of the new peak is smaller than that of maximum peak which exists in the diffraction angle 2theta=8.5 to 9 of X ray diffraction spectrum. The support component has 10-300mum average particle diameter. The solid catalyst component is used for polymerizing >=3C olefin which may contain silicon or copolymerizing the olefin with ethylene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a solid catalyst component for olefin polymerization. More specifically, for the polymerization of olefins suitable for gas phase polymerization, which have a relatively large particle size and are spherical, and which are excellent in crush resistance during polymerization and which may contain silicon having 3 or more carbon atoms, or One of the olefins
The present invention relates to a method for producing a solid catalyst component for copolymerizing ethylene with at least one species.

[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 has a good shape, has a relatively large particle size, and is resistant to crushing during polymerization. And has a problem that it is insufficient as a gas phase polymerization solid catalyst component for olefins, which is desired to have a property of being capable of obtaining an olefin polymer having high stereoregularity with high polymerization activity. It was

The inventors of the present invention have solved the above problems of the prior art and have proposed gas phase polymerization of olefins which may contain silicon having 3 or more carbon atoms, or gas phase polymerization of one or more of these olefins with ethylene. The inventors have earnestly studied to invent a method for producing an olefin polymerization catalyst component suitable for copolymerization. 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. It was found that the problem of the above-mentioned prior art can be solved when the above is used as a solid catalyst component for olefin polymerization, and the present invention has been completed based on this finding.

As is apparent from the above description, the object of the present invention is to have a good shape suitable for gas phase polymerization of olefins,
Provided is a method for producing a solid catalyst component for olefin polymerization, which has a relatively large particle size, is excellent in crush resistance during polymerization, and can obtain an olefin polymer having high stereoregularity with high polymerization activity. There is.

[0009]

The present invention includes the following (1).
To (3). (1) Mixture of magnesium compound and alcohol (A)
Is sprayed into a spray tower in a molten state, and at this time, the interior of the spray tower is cooled to a temperature at which the solid ingredient (B) can be obtained without substantial evaporation of alcohol, to obtain the solid ingredient (B). The alcohol is partially removed from the solid component (B) to obtain the solid component (C), and then the solid component (C) is contacted with the halogen-containing titanium compound (D) and the electron donor (E) to obtain the final component. In the method for obtaining the solid component (F) which is a solid catalyst component for olefin polymerization, the composition formulas of the mixture (A) and the solid component (B) are MgCl ₂
· MROH (where, R represents an alkyl group having 1 to 10 carbon atoms, m = 3.0 to 6.0.) Is indicated by, and the composition formula of the solid component _(C), MgCl 2 · nROH (However, R represents an alkyl group having 1 to 10 carbon atoms, and n = 0.
It is 4 to 2.8. ), The solid component (C)
In the X-ray diffraction spectrum of No. 1, as 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 °, or even if it is generated, the intensity of the new peak Is less than or equal to the intensity of the maximum peak existing at the diffraction angle 2θ = 8.5 to 9 degrees of the X-ray diffraction spectrum of the solid component (C), and the method for producing a solid catalyst component for olefin polymerization. (2) The production method according to (1), wherein the solid component (F) has an average particle diameter of 10 to 300 μm. (3) The above-mentioned (1), wherein the solid catalyst component for olefin polymerization is for polymerization of an olefin having 3 or more carbon atoms which may contain silicon, or for copolymerization of one or more kinds of the olefin and ethylene. Production method.

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 method of 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 M
gCl ₂ · mROH (wherein R represents an alkyl group having 1 to 10 carbon atoms) is mixed so that m is 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, the resulting solid catalyst component for olefin polymerization will have problems such as deterioration in shape and olefin polymerization activity. Also, m is 6.0.
If it exceeds, the crush resistance of the obtained solid catalyst component for olefin polymerization 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 for olefin polymerization and reduction of olefin polymerization activity occur. Further, if the heating temperature is too high, the crush resistance of the obtained solid catalyst component for olefin polymerization 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 according to the method of the present invention is carried out in a cooled spray tower, which cooling is usually a cooled inert gas or a cooled inert liquid fluid such as liquid nitrogen. It is carried out by introducing it into the 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. Said cooling is the temperature at which solid component (B) is obtained without substantial evaporation of alcohol,
That is, it is necessary to perform the treatment to a temperature at which the composition formula of the mixture (A) of magnesium chloride and alcohol and the solid component (B) does not change. Therefore, the inside of the spray tower is usually -70 to
10 ° C, preferably -50 to 0 ° C, particularly preferably -4
It is 0 to -5 ° C. If the cooling temperature is too high, the evaporation of alcohol will occur, and the particle shape of the obtained solid component (B) will be poor and 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 present invention, following the above steps, the solid component (C) is obtained by partially removing the alcohol from the obtained solid component (B). 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 next contact step with titanium halide, and the obtained solid catalyst component for olefin polymerization contains amorphous fine powder particles. The crush resistance deteriorates.

The solid component (C) according to the method of the present invention is not sufficient to achieve the object of the present invention if only the above-mentioned conditions are satisfied, and further the X-ray diffraction spectrum of the solid component (C). In comparison with the X-ray diffraction spectrum of the solid component (B), no new peak is generated at the diffraction angle 2θ = 7 to 8 °, or even if it is generated, the intensity of the new peak is It is necessary that the intensity is less than or equal to the maximum peak existing at a diffraction angle 2θ of 8.5 to 9 degrees in the X-ray diffraction spectrum of (C). At the diffraction angle 2θ = 7 to 8 degrees,
If a new large peak exceeding the intensity of the peak existing at a diffraction angle 2θ of 8.5 to 9 degrees is generated, the crush resistance of the obtained solid catalyst component for olefin polymerization 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 (E) 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.

As the electron donor (E) which is brought into contact with the solid component (C), an organic compound having at least one atom of oxygen, nitrogen, sulfur and phosphorus is used. Above all,
An electron donor such as an ether, an alcohol, an ester, an aldehyde, a fatty acid, a ketone, a nitrile, an amine, an amide, an isocyanate, a phosphine, a phosphite, a phosphinite, an acid anhydride, or an organic silicon compound having a Si—O—C bond is used. . Of these electron donors, esters are preferably used. Specifically, ethyl acetate,
Aliphatic monocarboxylic acid esters such as vinyl acetate, isobutyl acetate, octyl acetate, cyclohexyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, methyl toluate, toluic acid Ethyl, amyl toluate, ethyl ethyl benzoate, methyl anisate, aromatic monocarboxylic acid esters such as ethyl anisate, diethyl succinate, dibutyl succinate, diethyl methyl malonate, diethyl ethyl malonate, diethyl butyl malonate, Aliphatic polycarboxylic acid esters such as dibutyl maleate, dioctyl maleate, diethyl butyl maleate, diethyl itaconate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisophthalate Propyl 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 (E) are used. Most preferred are aromatic polycarboxylic acid esters.

When the solid halogen component-containing titanium compound (D) and the electron donor (E) are brought into contact with the solid component (C), the solvent (S2) need not be used if the contact treatment conditions are selected. Although not critical, the solid catalyst component for olefin polymerization, which is the final solid component (F), is controlled by controlling the reaction when the halogen-containing titanium compound (D) and the electron donor (E) are contacted with the solid component (C). It is a desirable aspect of the present invention to use the solvent (S2) from the viewpoint of preventing the deterioration of the particle shape, the generation of fine particles, and the reduction in crush resistance. 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 (E) and the solvent (S2) used are shown below. MgC in solid component (C)
The halogen-containing titanium compound (D) is used in an amount of 1 to 100 mol, preferably 3 to 50 mol, per 1 mol of l ₂ . The electron donor (E) is 0.01 to 1.0 mol, preferably 0.01 to 1.0 mol, based on 1 mol of MgCl ₂ in the solid component (C).
Use 0.8 mole. The solvent (S2) is 0 to 100 dm ³ , preferably 5 to 1 kg of the solid component (C).
Use ~ 70 dm ³ .

The order of contacting the halogen-containing titanium compound (D) and the electron donor (E) with 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 (E) is preferable. Further, a method of bringing the halogen-containing titanium compound (D) into contact after the contact with the electron donor (E) is also a preferred embodiment of the present invention.

As the conditions for contacting the halogen-containing titanium compound (D) and the electron donor (E) with the solid component (C), the contact temperature is −20 to 200 ° C., preferably 0.
To 200 ° C, most preferably 30 to 150 ° C, and the contact time is 5 minutes to 20 hours, preferably 10 minutes to 15
Time, most preferably 10 minutes to 10 hours.

After the contact of the halogen-containing titanium compound (D) and the electron donor (E) with the solid component (C) is completed, the solid obtained is separated by a method such as filtration or decantation, and then the solid is obtained. The separated solid is washed with an active hydrocarbon solvent (S3) to remove unreacted substances, by-products and the like to obtain a solid component (F), which is the final solid catalyst component for olefin polymerization, which is the object of the present invention. 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.

Thus, the average particle size of the obtained solid component (F) depends on the average particle size of the solid component (C), and although the particle size may be reduced to some extent in the subsequent step, it is usually the solid component. The average particle diameter of 90 to 100% of the average particle diameter of (C) is shown. Here, the average particle size of the solid component (F) that is preferable for achieving the object of the present invention is 10 to 300 μm, and more preferably 15 to 200 μm.

The solid component (F) obtained by the above-mentioned method of the present invention contains an organoaluminum compound (AL) and, if necessary, an electron donor (E2) as in the known solid catalyst component for olefin polymerization. Used in combination as a catalyst for the polymerization of olefins, or more preferably as a catalyst pre-activated by reacting a small amount of the olefins with the catalyst and used for the polymerization of olefins.

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 ≤3. ) 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 Such as monoalkyl aluminum dihalide may be mentioned, such as de, it can 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 above as the electron donor (E) are used, and particularly preferred are compounds having a Si—O—C bond. Specifically, methyltrimethoxysilane,
Methyltriethoxysilane, t-butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methylethyldimethoxysilane, dimethyldimethoxysilane,
Examples thereof include dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane and trimethyltriethoxysilane. 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 (AL1) is used so that 1 atom is 1 to 2000 mol, preferably 5 to 1000 mol.
The electron donor (E2) is used in an amount of 0 to 10 mol, preferably 0.01 to 5 mol, per 1 mol of Al atom in the organoaluminum compound (AL).

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. At the time of 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 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, an olefin polymer having high stereoregularity can be obtained. Further, these olefins are not only homopolymerized, but also combined with each other with other olefins such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or propylene, ethylene, and butene-. It is also possible to carry out copolymerization by combining three components as in 1,
Further, block copolymerization can be carried out by changing the kind of olefin fed in multistage polymerization.

[0040]

EXAMPLES The present invention will be described in more detail with reference to examples. The definitions of terms used in Examples and Comparative Examples and the measuring methods are as follows. (1) X-ray diffraction spectrum: Measured at a tube voltage of 50 KV and a tube current of 150 mA using an X-ray diffractometer JDX8200T manufactured by JEOL Ltd. in which the X-ray source is Cu-Kα ray. (2) Particle size distribution of solid component: Using a particle size distribution measuring device (Mastersizer MS20) manufactured by Malvern Instruments Ltd. by a laser light diffraction method, the solid component is dispersed in mineral oil to obtain the particle size distribution of the solid component. It was measured. (3) Average particle size: The particle size distribution is measured according to the above (2), the volume of the solid component for each particle size is integrated, and the particle size when the integrated volume is 50% of the total is shown. (Unit: μm) (4) Span: Similar to (3) above, the total volume is 9
The particle size at 0% is D _0.9 , and the cumulative volume is 10% of the total.
When the particle size at that time is represented by D _0.1 and the average particle system of (3) above is represented by D _0.5 , the following equation span = (D _0.9 −D _0.1 ) / D _0.5
Defined by It is an index showing the degree of particle size distribution. A large span indicates a wide particle size distribution, and a small span indicates a narrow particle size distribution. (5) Polymerization activity: 1 kg of solid catalyst component for olefin polymerization
The amount of polymerized olefin (kg) is shown and is a measure of olefin polymerization activity. (Unit: kg ・ Polymer / kg ・
Solid catalyst component) (6) BD: shows bulk density. (Unit: kg / m ³ )

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 for Olefin Polymerization 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 pressure 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 (E). 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, the} product was washed 3 times to obtain 6.0 kg of the final solid component (F) for olefin polymerization.
The obtained solid component (F) was spherical and had an average particle size of 11
At 5 μm, the span was 1.0. The titanium content of the solid component (F) was 2.0% by weight.

(3) Olefin Polymerization After a stainless reactor having an internal volume of 1.5 dm ³ equipped with a stirrer with inclined blades was replaced with nitrogen, CRYSTOL manufactured by Esso Oil Co., Ltd. was used as a saturated hydrocarbon solvent in the reactor.
-52 to 0.83 dm ³ , triethylaluminum 1
0.5 mmol, diisopropyldimethoxysilane 1.
6 mmol, and the solid component (F) 1 obtained in (2) above
After adding 4 g at room temperature, the mixture was heated to 40 ° C. and reacted at a propylene partial pressure of 0.05 MPa for 7 hours to obtain a preactivated catalyst. (Propylene 3.0 g per 1 g of the solid component (F)
reaction)

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 were removed was introduced, and 16.8 mg of the above pre-activated catalyst as a solid component (F), 1.4 mmol of triethylaluminum, and diisopropyldimethoxysilane. 0.14 mmol was added, and then 76 mmol of hydrogen was introduced, and then propylene gas was introduced to carry out gas phase polymerization of propylene under the conditions of 70 ° C. and pressure of 2.15 MPa in polymerization vessel for 2 hours (first time). polymerization). After polymerization, 30g of polypropylene particles in the polymerization vessel
After extracting the polymer so as to remain, 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). Such an operation was further repeated 4 times (third polymerization to sixth polymerization). The polymerization activity in the sixth polymerization was 16500 kg-polymer / kg-solid component (F), and BD was 420 kg / m ³ . The polymer obtained is spherical and has an average particle size of 2300μ.
and the finely divided polymer having a particle size of 210 μm or less was 0.01% by weight.

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

(2) Production of Solid Catalyst Component for Olefin Polymerization The conditions for partial removal of ethanol in 18.8 kg of the obtained solid component (B) are as follows: under reduced pressure of 267 Pa, at 60 ° C. for 2 hours. 3 hours at 70 ℃, 3.5 at 80 ℃
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) Olefin Polymerization A preactivated catalyst was obtained in the same manner except that the final solid catalyst component obtained in (2) above was used in place of the solid component (F) in (3) of Example 1. It was Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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

(2) Production of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, instead of the solid component (C), the solid component (B) obtained in the above (1) was dried under reduced pressure. 120 μm average particle size obtained by removing small particles smaller than 65 μm and particles larger than 180 μm using a sieve
8 out of 14.9 kg of solid component having m and span of 1.0.
4.1 kg of the final solid 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) Olefin Polymerization A pre-activated catalyst was 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 component (F). Obtained. Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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 component (F). .
Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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 component (F). .
Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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 component (F). .
Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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 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 component (F). .
Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

Table 1 shows the production conditions and polymerization 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 for Olefin Polymerization The solid component (B) obtained in (1) above was transferred to a vacuum dryer to partially remove ethanol in 21.9 kg, and the pressure 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.
I got 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 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 A pre-activated catalyst was prepared in the same manner as in Example 1 (3) except that the solid component (F) obtained in (2) above was used as the solid component (F). Got Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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.
It was 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 component (F). .
Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 2.

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) Production of Solid Catalyst Component for Olefin Polymerization The solid component (B) obtained in (1) above was transferred to a vacuum dryer for partial removal of ethanol in 20.5 kg, and the pressure 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 after sieving was used as the solid component (C), and the electron donor (E) was used. 5.5 kg of the solid 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 obtained solid component (F) had an average particle diameter of 118 μm and a span of 1.0.

(3) Production of olefin polymer Preliminary activation was carried out in the same manner as in Example 1 (3) except that the solid component (F) obtained in the above (2) was used as the solid component (F). A catalyst was obtained. Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

Table 2 shows the production conditions and polymerization 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 when the solid catalyst component for olefin polymerization obtained by the method of the present invention is used for olefin polymerization, it has a remarkably high polymerization activity without causing operational problems. Therefore, a highly stereoregular olefin polymer can be stably produced over a long period of time. As is clear from Examples 1 to 3 described above, the solid catalyst component for olefin polymerization 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 drawings]

1 is a solid component (B) for illustrating the method of the present invention.
FIG. 3 is an explanatory view 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 a solid catalyst component for olefin polymerization 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) collection pipe 13: Gas discharge pipe 14: Cyclone 15: Gas-entrained solid component (B) discharge pipe 16: Gas discharge pipe

Claims (3)

[Claims] 1. A mixture (A) of a magnesium compound and an alcohol in a molten state is sprayed into a spray tower, and 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 (E) are contacted with each other to obtain a solid component (F) which is a final solid catalyst component for olefin polymerization,
The composition formula of the mixture (A) and the solid component (B) is MgCl 2.
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. ), And in the X-ray diffraction spectrum of the solid component (C), the solid component (B)
Diffraction angle 2θ = 7 to 8 as compared with the X-ray diffraction spectrum of
The maximum peak present at the diffraction angle 2θ = 8.5 to 9 degrees of the X-ray diffraction spectrum of the solid component (C) even if it does not occur Or less, the method for producing a solid catalyst component for olefin polymerization. 2. The average particle size of the solid component (F) is 10 to 30.
The manufacturing method according to claim 1, wherein the manufacturing method is 0 μm. 3. The solid catalyst component for olefin polymerization is for the polymerization of an olefin having 3 or more carbon atoms which may contain silicon, or for the copolymerization of one or more of the olefins with ethylene. Manufacturing method.