JPH09176225A - Support for olefin polymerization catalyst component, olefin polymerization catalyst component and olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a highly stereoregular olefin polymer stably in high polymerization activity for a long time without any operational problem by using an olefin polymerization catalyst comprising an olefin polymerization catalyst component (component A), an organoaluminum compound and optionally an electron donor. SOLUTION: Component A is prepared by bringing a titanium halide compound (e.g. titanium tetrachloride) and an electron donor (e.g. aromatic polycarboxylic acid ester) into contact with a support for component A represented by formula I (wherein R is a 1-10C alkyl; and (n) is 0.4-2.8) and having an X-ray diffraction spectrum which, as compared with an x-ray diffraction spectrum of a solid component represented by formula II (wherein R is a 1-10C alkyl; and (m) is 3-6), has no new peak at a diffraction angle of 2θ of 7-8 deg. or has a peak of an intensity at most 2.0 times as high as that of the maximum peak appearing at a diffraction angle 2θ of 8.5-9 deg. in an aliphatic hydrocarbon solvent (e.g. isoparaffin mixture) having a boiling point of 90-180 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a carrier for an olefin polymerization catalyst component, an olefin polymerization catalyst component and an olefin polymerization catalyst. More specifically, a olefin polymerization catalyst suitable for gas phase polymerization, having a relatively large particle size and a spherical shape, and having excellent crush resistance during polymerization, an olefin polymerization catalyst component used for the catalyst, and the catalyst component The present invention relates to a carrier for an olefin polymerization catalyst component used.

[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. In particular, if the solid catalyst component does not have sufficient crush resistance, 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 or the fine powder polymer is entrained in unreacted olefins causes polymerization of the polymerization vessel. Olefin polymer from the inside of the polymerizer that flows out from the reactor and deposits unreacted olefin in the equipment such as the piping of the circulation system to the polymerizer and cooler, and eventually clogs the system, and deteriorates the powder flow characteristics. There is a problem in operation such that it becomes difficult to discharge.

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).

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.

Further, Japanese Patent Laid-Open No. 4-296305 discloses MgCl ₂ .3EtO obtained by a spray method.
A method for obtaining a solid catalyst component for olefin polymerization by reacting titanium tetrachloride at a relatively low temperature using an H carrier, then adding diisobutyl phthalate, and subsequently reacting in a nonane solvent under high temperature conditions. Is disclosed.

[0006] On the other hand, the applicant of the present invention has previously disclosed Japanese Patent Application Laid-Open No.
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

[0007]

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

The inventors of the present invention have solved the problems of the above-mentioned prior art, and have an olefin having 2 to 12 carbon atoms, particularly 3 carbon atoms.
The present invention is keen to invent a catalyst suitable for producing an olefin polymer by gas phase (co) polymerization of an olefin that may contain silicon or by gas phase copolymerization of one or more of the olefins with ethylene. Researched. 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, In a carrier having a specific X-ray diffraction spectrum obtained by removing a specific amount of alcohol from the solid component under the conditions of, a halogen-containing titanium compound and an electron in the presence of a solvent having a specific boiling point under specific temperature conditions. A final solid obtained by contacting a donor with a titanium halide compound is used as a solid catalyst component for olefin polymerization, and a catalyst obtained by combining this with an organoaluminum compound and, if necessary, an electron donor. It was found that the above-mentioned problems of the prior art can be solved by using the above method, and the present invention has been completed based on this finding.

As is clear from the above description, the object of the present invention is to have a good shape suitable for gas phase polymerization of olefins,
Olefin polymerization catalyst having a relatively large particle size, excellent crush resistance during polymerization, and capable of obtaining an olefin polymer having high stereoregularity with high polymerization activity, and olefin polymerization used for the catalyst It is intended to provide a catalyst component and a carrier for an olefin polymerization catalyst component used for the catalyst component.

[0010]

The present invention provides the following (1).
To (7). (1) Compared with the X-ray diffraction spectrum of the solid component (B) shown below, the X-ray diffraction spectrum shows a diffraction angle 2θ =
No new peak is generated at 7 to 8 degrees, or even if it occurs, the intensity of the new peak is 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. A carrier for an olefin polymerization catalyst component, which is less than or equal to 0.0 times and is represented by the following composition formula (I). MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. (2) Compared with the X-ray diffraction spectrum of the solid component (B) shown below, the X-ray diffraction spectrum has a diffraction angle 2θ =
No new peak is generated at 7 to 8 degrees, or even if it occurs, the intensity of the new peak is 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. The boiling point of the carrier for the olefin polymerization catalyst component represented by the following composition formula (I) is 90 to 180 ° C.
110 to 1 using an aliphatic hydrocarbon solvent (S) which is
An olefin polymerization catalyst component in which a halogen-containing titanium compound and an electron donor are contacted at a temperature of 35 ° C. MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. (3) The olefin polymerization catalyst component according to the above item 2, wherein the aliphatic hydrocarbon solvent (S) is an isoparaffin mixture. (4) The olefin polymerization catalyst component according to the above item 2, which has an average particle diameter of 10 to 300 μm. (5) An olefin polymerization catalyst comprising an olefin polymerization catalyst component shown below, an organoaluminum compound (AL), and optionally an electron donor (E2). Olefin polymerization catalyst component: X-ray diffraction spectrum has no or no new peak at diffraction angle 2θ = 7 to 8 degrees as compared with the X-ray diffraction spectrum of solid component (B) shown below. Also, the intensity of the new peak is 2.0 times or less than the intensity of the maximum peak existing at the diffraction angle 2θ of the X-ray diffraction spectrum 2θ = 8.5 to 9 °, and is represented by the following composition formula (I). Olefin polymerization in which a halogen-containing titanium compound and an electron donor are contacted at a temperature of 110 to 135 ° C. using an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. as a carrier for an olefin polymerization catalyst component Catalyst component. MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. (6) The olefin polymerization catalyst as described in 5 above, wherein the aliphatic hydrocarbon solvent (S) is an isoparaffin mixture. (7) The olefin polymerization catalyst according to the above item 5, which has an average particle size of 10 to 300 μm.

The structure and effect of the present invention will be described in detail below. In the present invention, the magnesium compound used for producing the olefin polymerization catalyst component is anhydrous magnesium chloride, and may contain a trace amount of water such that it is 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 can be mentioned. 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 olefin polymerization catalyst component carrier 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 such that m is 3.0 to 6.0 in the composition formula MgCl ₂ · mROH (where R represents an alkyl group having 1 to 10 carbon atoms). (Hereinafter referred to as a mixture of magnesium chloride and alcohol (A)
Is abbreviated. ) 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 it. The heating temperature is not particularly limited as long as it is equal to or higher than the temperature at which the mixture becomes a molten state, but is preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 110.
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. If the heating temperature is too high, the olefin polymerization catalyst component obtained will have poor crush resistance.

The mixture of the molten magnesium compound and the alcohol thus obtained is fed into 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 olefin polymerization catalyst component carrier used in the present invention is carried out in a cooled spray tower. 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 temperature in the spray tower is usually -70 to 10 ° C, preferably -50 to 0 ° C, and particularly preferably -40 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 bottom of the spray tower or the inert hydrocarbon solvent (S1) introduced into the lower part 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
-Used are 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. 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.

An embodiment of a 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.

The olefin polymer catalyst component carrier of the present invention is obtained by the solid component (B) obtained after the above steps.
Obtained by partial removal of alcohol. 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 olefin polymerization catalyst component carrier after the alcohol partial removal process is represented by the formula M
In gCl ₂ · nROH (where R represents an alkyl group having 1 to 10 carbon atoms), it is necessary to select the conditions for the alcohol partial removal step so that n falls within the range of 0.4 to 2.8. There is. 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.
It is. When n is less than 0.4, the olefin polymerization activity of the obtained solid catalyst component for olefin polymerization decreases. Further, when n exceeds 2.8, the olefin polymerization catalyst component carrier 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.

In addition to the above-mentioned conditions, the olefin polymerization catalyst component carrier of the present invention is required to satisfy the following conditions. That is, in the X-ray diffraction spectrum of the olefin polymerization catalyst component carrier, 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 degrees, or Even so, the intensity of the new peak is 2.0 times or less 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 olefin polymerization catalyst component carrier, and more preferably. Is 1.5 times or less in strength, particularly preferably 1.0 times or less. By satisfying the conditions, the crush resistance of the obtained olefin polymerization catalyst component is further improved.

In addition to the above-described conditions, the conditions for the above-mentioned alcohol partial removal step satisfying the above X-ray diffraction spectrum conditions are: avoiding rapid alcohol removal; 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 component (B) or the olefin polymerization catalyst component carrier flows is used, and the heating temperature is 0 to 100 ° C., preferably 10 under reduced pressure. ~
Under conditions of 80 ° C, most preferably 20-60 ° C,
The partial alcohol removal step is carried out for 1000 hours, preferably 3 to 500 hours.

In the method for producing an olefin polymerization catalyst component of the present invention, the olefin polymerization catalyst component carrier has a boiling point of 90.
The halogen-containing titanium compound and the electron donor in the presence of an aliphatic hydrocarbon solvent (S) at ˜180 ° C.
It is obtained by contacting under a temperature condition of 10 to 135 ° C.

The halogen-containing titanium compound to be brought into contact with the olefin polymerization catalyst component carrier 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, X represents a halogen, and u is an arbitrary number satisfying 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, dibutoxytitanium dichloride, diethoxytitanium dibromide, dibutoxytitanium dibromide, triethoxytitanium chloride and the like. One or more kinds of these halogen-containing titanium compounds are used. Most preferred is titanium tetrachloride.

As the electron donor (E1) which is brought into contact with the olefin polymerization catalyst component carrier, an organic compound having at least one atom of oxygen, nitrogen, sulfur and phosphorus is used. Among them, ether, alcohol, ester, aldehyde, fatty acid, ketone, nitrile, amine, amide,
An electron donor such as isocyanate, phosphine, phosphite, acid anhydride, or an organic silicon compound 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. Cyclohexyl,
Aromatic monocarboxylic acid esters such as methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl methyl malonate,
Diethyl ethyl malonate, diethyl butyl malonate, dibutyl maleate, dioctyl maleate, diethyl butyl maleate, diethyl itaconate, etc., aliphatic polycarboxylic acid esters, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, phthalic acid Di-n-propyl,
Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, diethyl terephthalate, naphthalene dicarboxylic acid. Examples thereof include aromatic polycarboxylic acid esters such as dibutyl acid. One or more of these electron donors are used. Most preferred are aromatic polycarboxylic acid esters.

When the halogen-containing titanium compound and the electron donor (E1) are brought into contact with the olefin polymerization catalyst component carrier, an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. is used. Here, the boiling point is 90 to 180 ° C.
Is a solvent whose vapor pressure is the standard atmospheric pressure (1.0
13-25 × 10 ⁵ Pa) is equal to 90 to 18
It means a solvent having a temperature of 0 ° C. Specific examples of such an aliphatic hydrocarbon solvent include saturated, unsaturated or halide compounds as long as the aliphatic hydrocarbon has a boiling point of 90 to 180 ° C., but n-heptane, n-octane, n
-Non-paraffins such as nonane and n-decane, 2,2
3,3-tetramethylbutane, 2-ethylpentane,
2,2,3-trimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-
Methylhexane, 3-methylhexane, 3-ethylhexane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3, Isoparaffins such as 4-dimethylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, etc., or a mixture thereof are preferably used, and a mixture of isoparaffins is particularly preferable. The mixture of isoparaffins is, for example, Isopar C (boiling point range: 97 to 1).
04 ° C) Isopar E (boiling point range: 116-142)
C.) and Isopar G (boiling point range: 160 to 174.degree. C.) are commercially available from Exxon Chemical Co., Ltd. and can be easily obtained.

The amounts of the olefin polymerization catalyst component carrier, the halogen-containing titanium compound, the electron donor (E1) and the solvent (S) used in the present invention are shown below. The halogen-containing titanium compound is 1 to 100 mol, preferably 3 to 1 mol of MgCl ₂ in the olefin polymerization catalyst component carrier.
Use 50 moles. The electron donor (E1) is 0.01 to 1 mol of MgCl ₂ in the olefin polymerization catalyst component carrier.
~ 1.0 mol, preferably 0.01-0.8 mol. The solvent (S) is 1 kg of the olefin polymerization catalyst component.
To 5 to 100 dm ³ , preferably 5 to 70 dm ³ .

The order of contacting the halogen-containing titanium compound and the electron donor (E1) with the olefin polymerization catalyst component of the present invention is not particularly limited, but after the solid component (C) is suspended in the solvent (S). A method is preferred in which the halogen-containing titanium compound is first contacted and then the electron donor (E1) is contacted.

As conditions for contacting the halogen-containing titanium compound and the electron donor (E1) with the olefin polymerization catalyst component carrier of the present invention, the contact temperature is 110 to 135.
C, preferably 115-135 C, most preferably 12
It is 0 to 135 ° C. If the contact temperature is too high or too low, the olefin polymerization activity of the obtained olefin polymerization catalyst component will decrease. The contact time is 5 minutes to 20 hours, preferably 10 minutes to 15 hours, most preferably 10 minutes to 1
0 hours.

In the above process, the solid component obtained by contacting the halogen-containing titanium compound and the electron donor (E1) with the olefin polymerization catalyst component carrier of the present invention (hereinafter referred to as the solid component (D)) (It may be abbreviated.)
Separated by a method such as filtration or decantation,
The halogen-containing titanium compound is subsequently contacted.

The halogen-containing titanium compound to be contacted with the olefin polymerization catalyst component of the present invention has the same general formula as that used for contacting the olefin polymerization catalyst component carrier of the present invention described above with Ti (OR ¹ ). _4-u X _u (where
R ¹ represents an alkyl group, a cycloalkyl group or an aryl group, and X represents a halogen. Further, u is an arbitrary number of 0 <u ≦ 4. ) A halogen-containing titanium compound represented by the formula (4) is used, and titanium tetrachloride is most preferably used.

In contacting the above-mentioned halogen-containing titanium compound with the olefin polymerization catalyst component of the present invention, it is more preferable to use the solvent (S2) in order to more effectively achieve the object of the present invention. is there. As the solvent (S2), those mentioned as the inert hydrocarbon solvent (S1) optionally used in the above-mentioned spray step, and the fat used when obtaining the olefin polymerization catalyst component of the present invention are used. The same hydrocarbon solvents as those listed as the group hydrocarbon solvent (S) can be used, but aromatic hydrocarbons such as benzene, toluene and xylene are preferably used, and toluene is particularly preferably used. Use of the solvent, in particular, aromatic hydrocarbon leads to the effect of further improving the olefin polymerization activity of the obtained olefin polymerization catalyst.

The amounts of the solid component (D), the halogen-containing titanium compound and the solvent (S2) used are shown below. The halogen-containing titanium compound is 1 to 100 mol, preferably 3 to 1 mol of MgCl ₂ in the solid component (D).
Use ~ 50 moles. The solvent (S) is 0 to 100 dm ³ , preferably 5 to 1 kg of the solid component (D).
Use ~ 70 dm ³ .

As the conditions for contacting the halogen-containing titanium compound with the solid component (D), the contact temperature is 110-110.
135 ° C., preferably 115-135 ° C., most preferably 120-135 ° C., contact time 5 minutes to 20 hours, preferably 10 minutes to 15 hours, most preferably 1
0 minutes to 10 hours.

After the contact of the halogen-containing titanium compound with the solid component (D) is completed, the solid obtained is separated by a method such as filtration or decantation, and the separated solid is washed with an inert hydrocarbon solvent (S3). Then, unreacted substances, by-products and the like are removed to obtain an olefin polymerization catalyst component which is the final solid catalyst component for olefin polymerization. As the inert hydrocarbon solvent (S3) used for washing, the same inert hydrocarbon solvent as the above-mentioned inert hydrocarbon solvent (S1) can be used.

Thus, the average particle size of the obtained olefin polymerization catalyst component depends on the average particle size of the carrier for olefin polymerization catalyst component of the present invention, and although the particle size may be reduced to some extent in the subsequent step, it is usually Shows an average particle size of 90 to 100% of the average particle size of the carrier for the olefin polymerization catalyst component. Here, the average particle size of the olefin polymerization catalyst component that is preferable for achieving the object of the present invention is 10 to 300 μm, and more preferably 15 to 200 μm.

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

The organoaluminum compound (AL) which is the organometallic compound catalyst component used in the olefin polymerization catalyst of the present invention has a general formula of AlR ² _p R ³ _q X _{3- (p + q)}
(In the formula, R ² and R ³ represent a hydrocarbon group or an alkoxy group such as an alkyl group, a cycloalkyl group and an aryl group, X represents a halogen, and p and q are any of 0 <p + q ≦ 3. An organoaluminum compound represented by a number is preferably 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 aluminum alkyls. Sesquihalide, ethyl aluminum dichlorate Examples thereof include monoalkylaluminum dihalides such as Cd and the like, and alkoxyalkylaluminums such as diethoxymonoethylaluminum can also be used. 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.

The electron donor (E2) optionally used as the olefin polymerization catalyst of the present invention is used for the purpose of controlling the stereoregularity of the olefin polymer obtained during ordinary olefin polymerization. Known electron donors that are used as necessary are used, specifically, the same electron donors as those mentioned as the above-mentioned electron donor (E1) are used, and Si-is particularly preferable. O-
It is a compound having a C bond. Specifically, methyltrimethoxysilane, methyltriethoxysilane, t-butyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyl Examples thereof include ethyldimethoxysilane, dimethyldimethoxysilane, 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 constituting the olefin polymerization catalyst of the present invention is the same as in the case of using a known catalyst component in combination as an olefin polymerization catalyst for olefin polymerization. Specifically, 1 atom of Al atom in the organoaluminum compound (AL) is contained in 1 to 20 mol of Ti atom in the solid catalyst component obtained by the method of the present invention.
The amount of the organoaluminum compound (AL1) is 00 mol, preferably 5 to 1000 mol, and the electron donor (E2) is 0 to 10 mol, preferably 1 mol of the Al atom in the organoaluminum compound (AL). Is 0.01 to 5
Use moles.

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.

The olefin polymerization catalyst component for olefin polymerization by the above-mentioned method of the present invention, the organoaluminum compound (AL), and, if necessary, the electron donor (E2).
The olefin polymerization method of the present invention in which the catalyst is used in combination with the catalyst of the present invention, or the catalyst in which a small amount of olefin is reacted with the catalyst to preactivate the catalyst is not limited, and the olefin polymerization method such as suspension polymerization or bulk polymerization performed in a solvent is not limited. It is also suitable for liquid phase polymerization, but when used for gas phase polymerization, the advantages of the olefin polymerization catalyst according to the method of the present invention are particularly exhibited. Further, in the polymerization of the olefin, it is preferable to use a preactivated catalyst.

The pre-activation is carried out in the presence of a catalyst obtained by combining the above-mentioned catalyst components with 0.05 g to 5,000 g of olefin per 1 g of the olefin polymerization catalyst component.
Preferably, 0.05 g to 3,000 g is used, and 0 ° C to
Olefin is reacted at 100 ° C. for 1 minute to 20 hours, and 0.01 g to 2,000 per 1 g of the olefin polymerization catalyst component.
It is desirable to produce g, preferably 0.05 g to 500 g of olefin polymer.

The catalyst thus obtained or the preactivated catalyst is used for the polymerization of olefins. The olefin polymerization conditions include a polymerization temperature of 20 to 150 ° C.
The polymerization pressure is 0.1 to 5 MPa, and usually 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 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. These olefins can be used not only in their respective homopolymerizations but also in the mutual combination with other olefins such as propylene, ethylene and butene.
-1 and ethylene, propylene and butene-1, or three components such as propylene, ethylene, and butene-1 can be used for copolymerization, and the type of olefin fed in the multi-stage polymerization can be changed. It is also possible to carry out block copolymerization.

[0046]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The definitions of terms used in Examples and Comparative Examples and measurement 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.
The particle size of the time D _0.1, a mean particle system of the above (3) defined by the following equation Span _{= (D 0.9 -D 0.1) /} D 0.5 when expressed as D _0.5. 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 carrier for olefin polymerization catalyst component First, a solid component (b) was produced using the apparatus shown in FIG. 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 into the stainless steel melting tank 4 having an internal volume of 60 dm ³ which was replaced with nitrogen. The composition was heated to 130 ° C. by passing heated steam through the jacket 5 while stirring this mixture, and the composition was MgCl 2.
A ₂ · 4.0EtOH mixture in a molten state: (a) 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 for maintaining this temperature during spraying and for cooling the inside of the spray tower 9. Was poured into a jacket 10 attached to the spray tower 9. The type of nozzle 8 is a small precision two-fluid nozzle (BN-90, manufactured by Shizuto Kyoritsu Shokai) and piping 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. After the solid component (b) and n-hexane were taken out of the system from the pipe 12, n-hexane was separated to obtain 18.8 kg of the solid component (b). From the obtained analysis result of the solid component (b), the composition of the 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.

An internal volume of 450 dm in order to partially remove the ethanol in 18.8 kg of the solid component (b) obtained.
^It was transferred to a vacuum dryer of ³ and under a reduced pressure of 267 Pa,
20 hours at 35 ° C, 4 hours at 45 ° C, followed by 5
After drying at 0 ° C. for 24 hours, 11.5 kg of a carrier for an olefin polymerization catalyst component was obtained. From the analysis results, the composition of the carrier for the olefin polymerization catalyst component was MgCl ₂ · 1.7 EtOH. With respect to the carrier for olefin polymerization catalyst component, small particles of less than 65 μm and particles larger than 180 μm were removed using a sieve to obtain 8.6 kg of carrier for olefin polymerization catalyst component having an average particle size 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. Further, a carrier for an olefin polymerization catalyst component (MgCl ₂ · 1.7 EtO) in which ethanol is partially removed
The X-ray diffraction spectrum of H) is shown in FIG. Diffraction angle 2θ
= No new peak appeared at 7 to 8 degrees.

(2) Manufacture of solid catalyst component for olefin polymerization Internal volume 110d equipped with condenser and filtration device
8.6 kg of a carrier for an olefin polymerization catalyst component, 37 dm ³ of Isopar E (manufactured by Exxon Chemical Co., Ltd.) which is an isoparaffin mixture, and 74 kg of titanium tetrachloride as a halogen-containing titanium compound were placed in a stainless steel reactor of m ³ . 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 127 ° 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 olefin polymerization catalyst component was obtained. The obtained olefin-polymerized solid catalyst component was spherical and had an average particle size of 115 μm.
The span was 1.0. The titanium content of the olefin polymerization solid catalyst component was 2.0% by weight.

(3) Production of Olefin Polymer After replacing a stainless reactor having an inner volume of 20 dm ³ equipped with a stirrer with an inclined blade with nitrogen, n-heptane was 18 dm ³ and triethylaluminum was 150 mm in the reactor.
ol, diisopropyldimethoxysilane 22 mmol,
Then, 180 g of the solid catalyst component (E) obtained in (2) above was added at room temperature, heated to 40 ° C., and then reacted at a propylene partial pressure of 0.03 MPa for 3 hours to obtain a preactivated catalyst. (Propylene 3. g / g of olefin polymerization catalyst component)
0g reaction)

Continuous horizontal gas phase polymerizer equipped with a stirrer having an internal volume of 110 dm ³ replaced with nitrogen (length / diameter = 3.
To 7), 25 kg of polypropylene powder (average particle size 1500 μm) from which polymer particles of 500 μm or less were removed was introduced, and 0.73 g / h of the above pre-activated catalyst as an olefin polymerization catalyst component, and triethylaluminum and diisopropyl. 15% by weight of dimethoxysilane
-The hexane solution was continuously supplied so that the molar ratio was 90 and 15 with respect to 1 mol of Ti atom in the olefin polymerization catalyst component. Further, hydrogen was supplied so that the ratio of the hydrogen concentration in the polymerization vessel to the propylene concentration was 0.02, and propylene was supplied into the polymerization vessel so that the pressure in the polymerization vessel was kept at 2.15 MPa. Gas phase polymerization was continuously performed for 150 hours. During the polymerization period, the polymer was withdrawn from the polymerizer at 11 kg / h so that the level of the polymer retained in the polymerizer was 60% by volume. The extracted polymer was subsequently subjected to contact treatment with nitrogen gas containing 5% by volume of steam at 100 ° C. for 30 minutes to obtain polypropylene particles. The polypropylene particles obtained at 140 hours after the initiation of the polymerization were spherical and had a BD of 440 kg /
m ³ , the average particle size was 2200 μm, and the finely divided polymer having a particle size of less than 210 μm was 0.05% by weight.

Comparative Example 1 (1) Production of Carrier for Olefin Polymerization Catalyst Component A carrier for olefin polymerization catalyst component was obtained in the same manner as in (1) of Example 1.

(2) Production of solid catalyst component for olefin polymerization In (2) of Example 1, toluene was used in place of Isopar E, and a carrier for olefin polymerization catalyst component, titanium tetrachloride, and diisobutyl phthalate were used. Contact temperature is 1
A solid catalyst component for olefin polymerization was obtained in the same manner except that the temperature was 20 ° C. The average particle size of the solid catalyst component is 115
μm, span was 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 olefin polymerization catalyst component was replaced with the final solid catalyst component obtained in the above (2). 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 2 (1) Production of Carrier for Olefin Polymerization Catalyst Component A carrier for olefin polymerization catalyst component was obtained in the same manner as in (1) of Example 1.

(2) Production of solid catalyst component for olefin polymerization In (2) of Example 1, n- was used instead of Isopar E.
A solid catalyst component for olefin polymerization was obtained in the same manner except that hexane was used and the contact temperature with the carrier for olefin polymerization catalyst component, titanium tetrachloride, and diisobutyl phthalate was 90 ° C. The average particle size of the solid catalyst component is 76
μm, span was 1.5.

(3) Production of Olefin Polymer A pre-activated catalyst was prepared in the same manner as in Example 1 (3) except that the final solid catalyst component obtained in (2) above was used in place of the olefin polymerization catalyst component. 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 3 (1) Production of carrier for olefin polymerization catalyst component A carrier for olefin polymerization catalyst component was obtained in the same manner as in (1) of Example 1.

(2) Production of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, Isopar G was used instead of Isopar E, and a carrier for olefin polymerization catalyst component, titanium tetrachloride, and diisobutyl phthalate were used. A solid catalyst component for olefin polymerization was obtained in the same manner except that the contact temperature was 140 ° C. The average particle size of the solid catalyst component is 1
It was 14 μm and the span was 1.0.

(3) Production of olefin polymer Preliminarily activated catalyst was prepared in the same manner as in Example 1 (3) except that the final solid catalyst component obtained in (2) above was used in place of the olefin polymerization catalyst component. 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 4 (1) Production of Carrier for Olefin Polymerization Catalyst Component Solid component (b) 18.8 in the same manner as in Example 1 (1)
kg. The conditions for partially removing ethanol in 18.8 kg of the obtained solid component (b) are as follows: under reduced pressure of 267 Pa, 60 ° C. for 2 hours, 70 ° C. for 3 hours, 8
The same procedure as in (1) of Example 1 was carried out except that the procedure was carried out at 0 ° C. for 3.5 hours to obtain 11.5 kg of a solid component. For the solid component, using a sieve, small particles of less than 65 μm and 180 μm
The larger particles were removed to obtain 6.9 kg of a solid component having an average particle size of 115 μm and a span of 1.2. Subsequently, the operation of obtaining the solid component (b), drying under reduced pressure, and sieving were separately repeated in the same manner to obtain 13.8 kg of the 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 3.0 times the intensity of the peak at the diffraction angle 2θ = 8.8 degrees.

(2) Manufacture of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, 8.6 kg of the solid component after sieving obtained by the above method is used instead of the carrier for olefin polymerization catalyst component. 6.0 kg of the final solid catalyst component was obtained in the same manner except that. The final solid catalyst component obtained had an average particle size of 80 μm and a span of 1.5.

(3) Production of Olefin Polymer A pre-activated catalyst was prepared in the same manner as in Example 1 (3) except that the final solid catalyst component obtained in (2) above was used in place of the olefin polymerization catalyst component. Got 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 the polymerization results of Example 1 and Comparative Examples 1 to 4 described above.

[0067]

[Table 1]

Comparative Example 5 (1), (2) A solid component (b) was obtained in the same manner as in (1) of Example 1. In (2) of Example 1, small particles of less than 65 μm and 1 using a sieve without drying the solid component (b) in place of the carrier for the olefin polymerization catalyst component under reduced pressure.
4.1 kg of the final solid catalyst component was similarly prepared except that 8.6 kg was used out of 14.9 kg of the solid component having an average particle size of 120 μm and a span of 1.0 obtained by removing particles larger than 80 μm. Obtained. The final solid catalyst component obtained was crushed, and the average particle size was 55 μm and the span was 1.8.

(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 the above step was used in place of the olefin polymerization catalyst component. 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) 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.

The solid component (12.3 kg) obtained in the above step was dried under reduced pressure using a sieve to remove small particles smaller than 65 μm and particles larger than 180 μm. The average particle size was 119 μm and the span was 1.1. Solid component 4.9 kg
was gotten. Subsequently, the above steps and sieving were separately repeated in the same manner to obtain 9.8 kg of solid components together.

(2) 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 (1) is used instead of the carrier for the olefin polymerization catalyst component. Thus, 6.6 kg of the final solid catalyst component 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 olefin polymerization catalyst component. 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) 8 kg of anhydrous MgCl ₂ , 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.

26.5 k of solid component obtained in the above (1)
Transferred to a vacuum dryer to partially remove the ethanol in g and under a vacuum of 267 Pa at 35 ° C. for 22 hours, 45
The solid was continuously dried at 6 ° C. for 6 hours and 53 ° C. for 20 hours to obtain 10.6 kg of a solid. From the analysis results, the composition of this solid is M
It was gCl ₂ · 1.7 EtOH. Subsequent removal of small particles below 65 μm and particles larger than 180 μm from the solid obtained using a sieve gave 8.9 kg of solid with a mean particle size of 120 μm and a span of 1.0.

(2) In Example 2 (2), except that 8.6 kg out of 8.9 kg of the solid after sieving obtained by the above method (1) is used in place of the carrier for the olefin polymerization catalyst component. In the same manner, the final solid catalyst component was 6.1 k
g was obtained. The average particle size of the final solid catalyst component obtained was 96.
The span was 1.4 in μm, and crushing occurred during the contact treatment of 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 olefin polymerization catalyst component. 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 8 (1) In the same manner as in (1) of Example 1, the solid component (b) 1
8.8 kg was obtained. 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 (1) 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-mentioned production of the solid component (b), drying under reduced pressure and sieving were separately repeated in the same manner to obtain 9.0 kg of the solid component in total.

(2) 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 (1) is used instead of the carrier for the olefin polymerization catalyst component. Thus, 8.4 kg of the final solid catalyst component 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 olefin polymerization catalyst component. 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 9 (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.

13.7k solid component obtained in the above process
In order to partially remove ethanol in g, 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, for the solid obtained, small particles smaller than 65 μm and 1
Particles larger than 80 μm are removed and the average particle size is 122 μm.
4.5 kg of a solid having a m and a span of 1.2 were obtained. Subsequently, the production of the above solid components, the drying under reduced pressure, and the sieving were separately repeated in the same manner to obtain 9.0 kg of solids.

(2) In the same manner as in (2) of Example 1, except that 8.6 kg of the solid after sieving obtained by the above method (1) is used instead of the carrier for the olefin polymerization catalyst component. Then, 8.4 kg of the final solid catalyst component was obtained. The final solid catalyst component obtained had an average particle size of 120 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 olefin polymerization catalyst component. Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

Example 2 (1) Production of carrier for olefin polymerization catalyst component 8 kg of anhydrous MgCl ₂ and 19.4 kg of dry ethanol
Was used, and spraying was performed 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) was .9 kg was obtained. From the analysis result 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 resulting solid component (b) had an average particle size of 100 μm and a span of 1.3.

Solid component (b) 2 obtained in the above step
Transferred to a vacuum dryer to partially remove ethanol in 1.9 kg and dried under reduced pressure of 267 Pa at 40 ° C. for 15 hours, further at 50 ° C. for 3 hours, and subsequently at 56 ° C. for 18 hours to perform olefin polymerization. 11.0 kg carrier for catalyst component
Obtained. From the analysis results, the composition of the carrier for the olefin polymerization catalyst component was MgCl ₂ · 1.5EtOH. About the carrier for the olefin polymerization catalyst component, 45μ using a sieve
Small particles smaller than m and particles larger than 150 μm were removed to obtain 8.7 kg of a carrier for an olefin polymerization catalyst component having an average particle diameter of 91 μm and a span of 1.0.

The above-mentioned carrier for olefin polymerization catalyst component (MgCl ₂ · 1.5 EtO) from which ethanol was partially removed.
H) was subjected to X-ray diffraction analysis. Although a new peak appeared at the diffraction angle 2θ = 7.6 degrees, its intensity was 1.5 times that of the peak at the diffraction angle 2θ = 8.8 degrees.

(2) Manufacture of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, as a carrier for olefin polymerization catalyst component, a carrier for olefin polymerization catalyst component after sieving obtained by the above method (1) Was used in the same manner as above, except that 5.9 kg of an olefin polymerization catalyst component, which was the final solid catalyst component for olefin polymerization, was obtained. The obtained olefin polymerization catalyst component had an average particle size of 88 μm and a span of 1.0.

(3) Production of Olefin Polymer A preactivation catalyst was obtained in the same manner as in Example 1 (3) except that the olefin polymerization catalyst component obtained in the above (2) was used as the olefin polymerization catalyst component. 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.

Example 3 (1) Production of carrier for olefin polymerization catalyst component 8 kg of anhydrous MgCl ₂ and 17.4 kg of dry ethanol
Spraying was performed in the same manner as in (1) of Example 1 except that the above 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 resulting solid component (b) had an average particle size of 130 μm and a span of 1.5.

Solid component (b) 2 obtained in the above process
Transferred to a vacuum dryer for partial removal of ethanol in 0.5 kg and dried under reduced pressure of 267 Pa for 19 hours at 35 ° C. for 19 hours, further at 45 ° C. for 4 hours, and subsequently at 50 ° C. for 24 hours for olefin polymerization. 13.5 kg of catalyst component carrier
Obtained. From the analysis results, the composition of the carrier for the olefin polymerization catalyst component was MgCl ₂ · 2.1 EtOH. About the carrier for the olefin polymerization catalyst component, 65μ using a sieve
Small particles smaller than m and particles larger than 180 μm were removed to obtain 10.2 kg of an olefin polymerization catalyst component carrier having an average particle size of 120 μm and a span of 1.0.

The carrier for the olefin polymerization catalyst component (MgC
The X-ray diffraction analysis of (1 ₂ · 2.1 EtOH) was performed. No new peak appeared at the diffraction angle 2θ = 7 to 8 degrees.

(2) Production of Solid Catalyst Component for Olefin Polymerization In (2) of Example 1, as the carrier for olefin polymerization catalyst component, 8 units of the carrier for olefin polymerization catalyst component after sieving obtained in (1) above were used. .6 kg, using n-heptane as a solvent instead of Isopar E, using di-n-butyl phthalate 1.8 kg as an electron donor instead of diisobutyl phthalate, and an olefin polymerization catalyst. 5.5 kg of the olefin polymerization catalyst component which is the final solid catalyst component for olefin polymerization was obtained in the same manner except that the contact temperature of the component carrier with titanium tetrachloride and di-n-butyl phthalate was 120 ° C. . The obtained olefin polymerization catalyst component has an average particle size of 118 μm.
And the span was 1.0.

(3) Production of Olefin Polymer A preactivation catalyst was prepared in the same manner as in (3) of Example 1 except that the olefin polymerization catalyst component obtained in the above (2) was used as the olefin polymerization catalyst component. Obtained. Using the obtained preactivated catalyst, vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

The above Comparative Examples 5 to 9 and Examples 2 to 3
Table 2 shows the production conditions and the results of polymerization.

[0096]

[Table 2]

[0097]

The main effects of the present invention are as follows: when the olefin polymerization catalyst of the present invention in which an olefin polymerization solid catalyst component, an organoaluminum compound and, if necessary, an electron donor are combined is used for olefin polymerization, A highly stereoregular olefin polymer can be stably produced over 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 for olefin polymerization 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 olefin polymer particles having a relatively large particle size, very little generation of fine powder polymer, and high bulk density with high polymerization activity. Is.

On the other hand, when the solid catalyst component shown in the comparative example is applied to olefin polymerization as a catalyst component for olefin polymerization, operational problems such as generation of fine powder polymer and low polymerization activity occur, and therefore high stereoregularity is obtained. It is impossible to stably produce a polymerizable olefin polymer (Comparative Examples 1 to 9).

[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.

[Explanation of Codes] 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 tube

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 carrier for an olefin polymerization catalyst component obtained in Example 1.

FIG. 4 shows an X-ray diffraction spectrum of the carrier for olefin polymerization catalyst component (MgCl ₂ · 1.7 EtOH) obtained in Comparative Example 4.

FIG. 5 is a flow sheet of an olefin polymerization catalyst for explaining the method of the present invention.

Claims (7)

[Claims] 1. The X-ray diffraction spectrum has a diffraction angle of 2 as compared with the X-ray diffraction spectrum of the solid component (B) shown below.
There is no new peak at θ = 7 to 8 degrees, or even if it occurs, the intensity of the new peak is the intensity of the maximum peak existing at the diffraction angle 2θ = 8.5 to 9 degrees of the X-ray diffraction spectrum. The carrier for the olefin polymerization catalyst component, which is 2.0 times or less of the above and is represented by the following composition formula (I). MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. ) 2. The X-ray diffraction spectrum has a diffraction angle of 2 as compared with the X-ray diffraction spectrum of the solid component (B) shown below.
No new peak is generated at θ = 7 to 8 degrees, or even if it is generated, the intensity of the new peak is the maximum peak intensity existing at the diffraction angle 2θ = 8.5 to 9 degrees of the X-ray diffraction spectrum. 2.0 times or less, and the boiling point of the carrier for the olefin polymerization catalyst component represented by the following composition formula (I) is 90 to 180.
110 ° C. using an aliphatic hydrocarbon solvent (S)
An olefin polymerization catalyst component in which a halogen-containing titanium compound and an electron donor are contacted at a temperature of 135 ° C. MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. ) 3. The olefin polymerization catalyst component according to claim 2, wherein the aliphatic hydrocarbon solvent (S) is an isoparaffin mixture. 4. The olefin polymerization catalyst component according to claim 2, which has an average particle size of 10 to 300 μm. 5. An olefin polymerization catalyst comprising an olefin polymerization catalyst component shown below, an organoaluminum compound (AL), and optionally an electron donor (E2). Olefin polymerization catalyst component: X-ray diffraction spectrum has no or no new peak at diffraction angle 2θ = 7 to 8 degrees as compared with the X-ray diffraction spectrum of solid component (B) shown below. Also, the intensity of the new peak is 2.0 times or less than the intensity of the maximum peak existing at the diffraction angle 2θ of the X-ray diffraction spectrum 2θ = 8.5 to 9 °, and is represented by the following composition formula (I). Olefin polymerization in which a halogen-containing titanium compound and an electron donor are contacted at a temperature of 110 to 135 ° C. using an aliphatic hydrocarbon solvent (S) having a boiling point of 90 to 180 ° C. as a carrier for an olefin polymerization catalyst component Catalyst component. MgCl ₂ · nROH composition formula (I) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and n =
It is 0.4 to 2.8. ) Solid component (B): A solid composition represented by the following composition formula II, which comprises a magnesium compound and an alcohol. MgCl ₂ · mROH composition formula (II) (wherein R represents an alkyl group having 1 to 10 carbon atoms, and m =
It is 3.0 to 6.0. ) 6. The olefin polymerization catalyst according to claim 5, wherein the aliphatic hydrocarbon solvent (S) is a mixture of isoparaffins. 7. The olefin polymerization catalyst according to claim 5, which has an average particle size of 10 to 300 μm.