JPS60192710A - Production of catalyst component for polyolefin production - Google Patents

Abstract

PURPOSE:To obtain the titled catalyst component having a high polymerization activity and providing a highly stereoregular polymer, by reacting a specified solid product with Ti and/or V halides and washing it with a liquid inert hydrocarbon. CONSTITUTION:A solution prepared by dissolving, with stirring and heating, 1mol of an anhydrous Mg dihalide, 0.005-0.7mol of an Al halide (e.g., AlCl3), 0.1-2mol of a titanate ester (e.g., ethyl orthotitanate), and 0.1-6mol of an alcohol (e.g., n-hexyl alcohol) in an inert hydrocarbon solvent is mixed and reacted with 0.1-50mol of a Si halide (e.g., SiCl4) and 0.05-0.7mol of an organic acid ester (e.g., ethyl acetate) to precipitate a solid product. A solid product obtained by reacting the above-produced solid product with Ti and/or V halides (e.g., TiCl4) is washed with a liquid inert hydrocarbon to obtain the titled catalyst component containing 50wt% or above liquid inert hydrocarbon.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a catalyst component for producing polyolefins. More specifically, the present invention provides a novel support for a supported Ziegler-Natsuta catalyst in which anhydrous magnesium cybaride, aluminum halide, titanate ester, and alcohol are once dissolved in an inert hydrocarbon solvent, and the resulting solution is dissolved. A solid product (1
).

However, in the present invention, polyolefins refer to tl of α-olefins having 3 or more carbon atoms and copolymers.
Alternatively, it is a copolymer of an α-olefin having 3 or more carbon atoms and an α-olefin having 2 carbon atoms, in which the former accounts for 50% by weight or more as a component ratio in the copolymer.

Conventionally, the direction of improvement of Chigun-Natsume type catalyst is as follows:
Catalysts that provide polymers with high polymerization activity and high stereoregularity have been actively pursued. However, in recent years, in addition to the above-mentioned performance, there has been a demand for a good particle shape of the resulting polymer.

The present inventors have already disclosed a method for producing polyolefins using a supported solid catalyst component that provides polymers with high polymerization activity, high stereoregularity, and good particle shape in Japanese Patent Application No. 5.8-189010. (hereinafter referred to as the prior invention).

The proposal differs from the present invention in that after obtaining the solid product (n) from anhydrous magnesium cybaride in the same manner as the present invention,
The solid product (II) is dried to an extent that almost no liquid inert hydrocarbon remains to form a solid powder, which is further prepolymerized to obtain a supported solid catalyst component, and the supported solid catalyst component is used to produce a polyolefin. This is a method of manufacturing. However, as a result of intensive studies aimed at simplifying the manufacturing process of supported solid catalyst components, the solid product of the earlier invention (I
It was found that the step of drying t) and the step of performing prepolymerization treatment can be omitted, leading to the present invention.

As is clear from the above description, the purpose of the present invention is to provide a catalyst component having polymerization performance equivalent to or better than that of the catalyst component according to the prior invention, and a method for producing the same, by a significantly simpler manufacturing method. Another object is to provide a method for producing a novel polyolefin using this catalyst component.

The present invention has the following main configuration (1).

(1) ■ Anhydrous magnesium cybaride, aluminum halide, titanate ester, and hyalcohol are mixed and dissolved in an inert hydrocarbon solvent, and ■ silicon halide and organic acid ester are added to the solution thus obtained. (1) to react with titanium halide and/or vanadium halide, and (2) react the solid after the nuclear reaction with liquid inert hydrocarbon. A catalyst component for polyolefin production, characterized in that the solid product (II) is obtained in the coexistence of at least 50% by weight of a liquid inert hydrocarbon. How to manufacture.

The configuration and effects of the present invention will be explained in detail below.

First, a method for manufacturing a supported solid catalyst on which a transition metal compound is supported will be described.

First, anhydrous magnesium cybaride, (organic) aluminum halide, titanate ester, and alcohol are mixed in an inert hydrocarbon solvent and dissolved by heating. As the anhydrous magnesium cybaride, anhydrous magnesium chloride and anhydrous magnesium bromide can be used. Anhydrous may include a compound containing a trace amount of water comparable to that of commercial products sold as these "anhydrous" compounds. As (organic) aluminum halide, AIXyLI'L%-
It is a compound represented by Y, where X is C1 and B.
r, R' is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms;
is the number of

Examples include aluminum trichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, dipropylaluminum chloride, triethylaluminum, aluminum tribromide, ethylaluminum dichloride, and the like. The titanate ester is an orthotitanate ester represented by Ti(OR2)4 and a polytitanate ester represented by R3moO-Ti(R")(R5)o-nF. Here, R+" , R,'', l'L', R' and R' are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, m is 2 to 2
The number is 0. Specifically, methyl orthotitanate, ethyl orthotitanate, lupropyl orthotitanate, lupropyl orthotitanate, 1-amyl orthotitanate,
Orthotitanate esters such as phenyl orthotitanate and cyclohexyl orthotitanate, polymethyl titanate, polyethyl titanate, luglovir polytitanate, 1-propyl polytitanate, rubyl polytitanate, i-butyl polytitanate, ruamyl polytitanate,
Polytitanate esters such as phenyl polytitanate and cyclopentyl polytitanate can be used.

As the alcohol, aliphatic alcohols can be used. Specifically, methyl alcohol, ethyl alcohol, lupropyl alcohol, i-propyl alcohol, lupropyl alcohol, i-amyl alcohol,
In addition to monohydric alcohols such as ruhexyl alcohol, ruheptyl alcohol, ruoctyl alcohol, and 2-ethylhexyl alcohol, ethylene glycol,
Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, carbon number 4-1
0 aliphatic alcohols are preferred.

Inert hydrocarbon solvents include pentane) aliphatic hydrocarbons such as hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Silicon halides such as can be used. Among them, aliphatic hydrocarbons are preferred. Specifically, the method for dissolving is: ■ Mixing anhydrous magnesium cybaride, (organic) aluminum halide, titanate ester, and alcohol in an inert hydrocarbon solvent in any order of addition, and stirring the suspension. Heat to dissolve the titanate ester and alcohol in an inert hydrocarbon solvent with stirring, and add anhydrous magnesium cybaride and aluminum halide to the solution and dissolve; or ■ Anhydrous magnesium cybaride and the halogen. Examples of the method include suspending (organic) aluminum chloride in an inert hydrocarbon solvent while heating it, and adding and dissolving titanate ester and alcohol to the suspension. Although any method can be employed, method (2) is preferred because it is extremely easy to operate. The solution after heating may be completely dissolved to become a homogeneous solution, or a small amount of insoluble matter may remain. However, if a small amount of insoluble matter remains, it may not adversely affect the particle shape of the solid catalyst, so it is preferable to completely dissolve it to form a homogeneous solution. In some cases, even a small amount of insoluble matter is extremely difficult to dissolve even after a long period of time. In such a case, a small amount of insoluble matter may be separated in a furnace to form a homogeneous solution. Heating is required to dissolve it. The temperature is 40-200℃, preferably 50-15℃
It is 0°C. The time is 5 minutes to 7 hours, preferably 10 minutes to
It is 5 hours.

The amount of (organic) aluminum halide used is 0.005 to 0.7 per 1 mol of anhydrous magnesium cybaride.
mol, preferably 0.01 to 0.5 mol, and the amount of titanate to be used is 0.1 to 2.0 mol, preferably 0. 5-1
．． It is 5 mol. In the case of polytitanate ester, pay attention to the repeating unit of orthotitanate ester in the polytitanate ester molecule, convert the unit equivalent to orthotitanate ester to ynol unit, and determine the usage amount in the same way as in the case of orthotitanate ester. good. The amount of alcohol used is 0.1 to 6 mol, preferably 0.5 to 5 mol, per 1 rILol of anhydrous magnesium cybalide.

The greater the amount of titanate ester and alcohol used relative to anhydrous magnesium sybaride, the greater the solubility of anhydrous magnesium sybaride in an inert hydrocarbon solvent. Moreover, re-solidification itself is difficult, and even after solidification, it is extremely difficult to control the particle shape. Furthermore, if the amounts of titanate ester and alcohol used are too small, the anhydrous magnesium cybaride will not be soluble in the inert hydrocarbon solvent, and the solid catalyst will become amorphous, making it impossible to achieve the object of the present invention.

The amount of the inert hydrocarbon solvent used is 0.1 to 511, preferably 0 to anhydrous magnesium cybaride l not.
．． 3 to 31. - In most cases, solids do not precipitate out of the solution after dissolving it to room temperature, so it can be stored as a homogeneous solution at room temperature.

Next, a silicon halide and an organic acid ester are reacted in the above solution to obtain a solid product (1).

The method for obtaining the solid product (1) is as follows: (1) adding an organic acid ester to the solution containing magnesium halide and causing a reaction; (2) adding silicon halogenide to precipitate a solid; A solid can be obtained by adding silicon halide and reacting to precipitate a solid, or by adding silicon halide to precipitate a solid and then adding an organic acid ester and reacting, or a combination of these methods. After that, the solid is washed with an inert hydrocarbon solvent to obtain the solid product (1). Organic acid esters, aliphatic carboxylic acid esters such as Teha, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl propionate and ethyl butyrate, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, anise Aromatic carboxylic acid esters such as methyl acid and ethyl anisate. As silicon halides, 8iXIR″4.g and S 1X
A compound represented by p(OR'), -P can be used. Here, X is C! Alternatively, Brs'l'L' and R8 are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and hb, 1 and P are numbers of 1 to 4. Specifically, 8iX and 5R-7 include silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, and ethyl silicon tribromide. , diethyl silicon dichloride, diptylsilicon dichloride, triethyl silicon chloride, and the like can be used.

81Xp (OR”) 4□ includes silicon tetrachloride, silicon tetrabromide, silicon trichloride, propoxy silicon trichloride, butoxy silicon trichloride, silicon trichloride ethoxy, silicon tribromide, jetoxy silicon dichloride ,
Dibutoxy silicon dichloride, triethoxy silicon chloride, etc. can be used.

It is also possible to use mixtures of the compounds mentioned above.

Among them, silicon tetrachloride is preferred. The organic acid ester and silicon halide may be used as they are or after being diluted with a solvent.

In that case, the same solvent as the inert hydrocarbon solvent mentioned above can be used. It is preferable to react the organic acid ester by adding it to a solution containing magnesium halide separately from the silicon halide or in the coexistence of the silicon halide, but the silicon halide may be added to the solution or It may also be added to silicon halides.

The total amount of organic acid ester used is 0.05 to 0.7 mol per 1 mol of anhydrous magnesium oxide.

Preferably it is 0.1 to Q, 5 mol. This amount of organic acid ester may be used all at once, or may be used in several stages. The reaction temperature is 30-isoC, preferably 50-130C, and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours per step.

Even if only an organic acid ester is added to a solution containing magnesium halide and reacted, no solid will precipitate, but if left at high temperatures for a long time, the organic acid ester will change to another compound, resulting in the final product. The role of stereoregularity control on the solid product (1) may be reduced. The reaction with silicon halide is carried out at a temperature of 40 to 150°C, preferably 50 to 130°C, and for a time of 5 minutes to 10 hours, preferably 10 minutes to 5 hours. The amount of silicon halide used is 0.1 to 50 mol per anhydrous magnesium cybaride used. Preferably 1 to 20 ynol
It is. By adding silicon halide and causing a reaction, a solid will precipitate. Since the particle shape of the solid product (II) is controlled by the particle shape of the solid product (1), the reaction between the solution and the silicon halide described above is extremely important for controlling the particle shape.

After the organic acid ester and the silicon chloride are reacted, the reaction with the titanium chloride may be performed subsequently, but the precipitated solid should be washed with the above-mentioned inert hydrocarbon. It is preferable. This is because unreacted substances or by-products present in the solution may prevent subsequent reactions.

A solid product (1) is thus obtained.

Next, solid product (1) is reacted with titanium halide and/or vanadium halide to produce solid product (n
). As titanium chloride, T +
A compound represented by q (OR") 4 q can be used. Here, q is a number from 1 to 4. Specifically, titanium tetrachloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, octanoxytitanium trichloride, phenoxytitanium trichloride, cyclohexyne trichloride Examples include titanium oxytitanium, jetoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, triethoxytitanium chloride, and triphenoxytitanium chloride.Titanium halides other than titanium tetrachloride are titanium tetrachloride. It can be produced by the reaction between titanium tetrachloride and orthotitanate, but a mixture of titanium tetrachloride and orthotitanate can also be used in this reaction.As orthotitanate, the above-mentioned orthotitanate and The same material can be used. Among these titanium halides, titanium tetrachloride is most preferred. Specific examples of vanadium halides include vanadium tetrachloride, vanadium oxytrichloride, and vanadium containing at least one halogen. Other vanadium conductors combined with titanium halides and/or
Alternatively, vanadium chloride can be used as it is or diluted with a solvent. The solvent in this case may be the same as the inert hydrocarbon solvent described above.

The reaction between the solid product (1) and titanium halide is as follows: (1)
) Adding titanium halide to a suspended solution of solid product (1) or adding solid product (I) into the titanium halide
) and react. Alternatively, (2) the solid product (1) is washed with phlegm by door-to-door or decantation method, and the solid product (1) is suspended in the above-mentioned inert hydrocarbon solvent; For example, a titanium halide is added or a suspension of the solid product (1) is added to the titanium halide and reacted. The same applies when vanadium halide is used instead of titanium halide or together with titanium halide. Among them, method (2) is preferred.

The amount of titanium halide or vanadium halide used is 1 to 100 mol, preferably 3 to 59 mol, per rnol of anhydrous magnesium dinoride.

The reaction temperature of the solid product (1) and titanium chloride or vanadium chloride is 40 to 150°C, preferably 50 to 130°C, and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours. It is. After the reaction, the solid is separated by door to door or decantation method and washed with an inert solvent to remove unreacted substances or by-products. A solid product (n) is thus obtained. The solid product (II) of this stage
The particle shape of the particles must be good.

The solvent used during cleaning is a liquid inert hydrocarbon.

Specifically, hexane, heptane, octane, nonane,
Mention may be made of aliphatic hydrocarbons such as decane or kerosene. During and after washing, solid products (If
) must coexist with at least 50% by weight of the above-mentioned liquid inert hydrocarbon. The washing method is particularly preferably a decantation method, and after washing, at least an amount of liquid inert hydrocarbon coexists with the solid product (n) such that the solid product (II) is immersed in the liquid inert hydrocarbon. It is preferable to do so. If only 50% by weight of liquid inert hydrocarbon coexists with respect to the solid product (n), sufficient catalyst may be obtained even if the solid product (II) is combined with the organoaluminum compound and then subjected to polymerization. Does not perform well.

That is, the polymerization results are low in polymer yield and bulk specific gravity, poor in shape, large in amount of fine powder, and low in stereoregularity. It is important to store the washed solid product (II) in the coexistence of at least 50% by weight of a liquid inert hydrocarbon and to subject it to polymerization.

The solid product ([) can be combined as a solid catalyst component with an organoaluminum compound and preferably an organic acid ester to form a catalyst for the production of α-olefin polymers. As the organic aluminum compound to be combined, AA! A compound represented by X5R'Q can be used. Here, X is C11R" is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and S is a number of θ to 2. Specifically, triethylaluminum,) !J-7L-Propyl aluminum, treaty butyl aluminum, tricyclopentyl aluminum, tricyclohexyl aluminum, dimethyl aluminum chloride, diethylaluminum chloride, di-butyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc. Among them, triethylaluminum alone, a mixture of two types of organoaluminum compounds such as triethylaluminum and tri-butylaluminum, triethylaluminum and diethylaluminum chloride, and triethylaluminum and ethylaluminum sesquichloride, or triethylaluminum and tri-l-butylaluminum It is preferable to use a mixture of three types of organoaluminum compounds such as aluminum and ethylaluminum sesquichloride.

As the organic acid ester, the same compound as the organic acid ester used in the step of producing the complex compound can be used. Among these, aromatic carboxylic acid esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate are preferred.

As a method for combining the solid product (II), an organoaluminum compound, and an organic acid ester, ■ solid product (I
I), feeding the organic aluminum compound and the organic acid ester independently to the polymerization vessel, ■ feeding the mixture of the organic aluminum compound and the organic acid ester and the solid product (1) independently to the polymerization vessel, ■ supplying the solid product ( (2) There are embodiments such as supplying a mixture of an organoaluminum compound and an organic acid ester to a polymerization vessel, and any of these methods can be adopted.

However, among these, there are cases where ■ is still preferable.

When combining the three components as described above, each component or any one of the components may be dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane, and kerosene. . ■
When mixing before supplying to the polymerization vessel as in (1) and (2), the temperature is -50 to +50°C, preferably -30 to +30°C,
The time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of organoaluminum compound used is the titanium atom contained in the solid product (1) as a solid catalyst component.
10 to 1000 mol, preferably 50 to 1000 mol per l
5 Q Q mol. The amount of organic acid ester used is 0, Q 1 per 1 mol of organoaluminum compound.
~1 mol, preferably 0.05-0.7 mol. When using a mixed organic aluminum compound or a mixed organic acid ester, the total number of moles thereof should fall within the above-mentioned range.

Solid product (n) as solid catalyst component according to the invention,
Using a catalyst obtained by a combination of an organoaluminum compound and preferably an organic acid ester, an α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms. As the α-olefin having 3 or more carbon atoms, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1, 3-methylpentene-1, etc. are used. be able to.

The polymerization of these α-olefins includes not only homopolymerization but also copolymerization with one or more other α-olefins having 2 or more carbon atoms. Carbon number 2
Examples of the above α-olefins include ethylene, butadiene, isoprene, 1,4-pentadiene, and the like, in addition to the above-mentioned α-olefins having 3 or more carbon atoms. The amount of these other α-olefins used is such that the copolymer obtained by copolymerization contains 3Qmo1% or less. Polymerization can be carried out in the liquid phase or in the gas phase. If the polymerization is carried out in the liquid phase, an inert hydrocarbon solvent such as, for example, hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may also be used as the reaction medium. can. When polymerization is carried out in the gas phase, no reaction medium is used in principle, but it is also possible to use the catalyst or any of its components dissolved or suspended in the above-mentioned inert hydrocarbons. Polymerization is carried out in a polymerization vessel by bringing the catalyst and the α-olefin into contact with each other. Polymerization temperature is 40
-200°C, preferably 50-150°C, polymerization pressure is atmospheric pressure -100 kg/cIIG, preferably 5-5
0kg/cI1. It is G. Polymerization can be carried out in a batch, semi-continuous or continuous manner, but continuous polymerization is preferred industrially.

It is also possible to perform the polymerization by multistage polymerization using different polymerization conditions. In order to control the molecular weight of the polymer, it is effective to add a molecular weight regulator such as hydrogen to the polymerization system.

The above-mentioned production or storage of solid catalyst components, preparation of catalysts, and production of polymers must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases they may be carried out under an atmosphere of 70% or under vacuum conditions. But it can be done.

The main effects of the present invention are as follows. First, it has extremely high polymerization activity, and there is no need to remove residual catalyst from the polymer. It is extremely economical as there is no need for a polymer purification step. Second, the stereoregularity of the polymer is extremely high.

This is indicated by the high isotactic index (hereinafter abbreviated as II). It is extremely advantageous for producing polymers by gas phase polymerization without using solvents. Furthermore, a characteristic effect of the present invention is that the particle shape of the obtained polymer is extremely good. In other words, the shape of the polymer particles is spherical or nearly spherical, and it is possible to control the polymer particle size to a predetermined size and the polymer particle size distribution to be extremely narrow. In other words, there are very few small polymers, that is, fine powders. This allows stable production operation of the polymerization vessel for a long period of time in liquid phase polymerization methods and gas phase polymerization methods such as slurry polymerization and bulk polymerization. In addition, industrially, the polymer according to the present invention can be easily transported and recovered during the manufacturing process, and the feeding to a granulator and processing and molding operations are easy, and the productivity per industrial polymerization device is high. Much improved.

It can suppress dust explosions caused by fine powder and is effective in preventing entrainment.

Further, even when α-olefin is copolymerized in the method of the present invention, there is little deterioration in the shape of the polymer particles or a decrease in the bulk specific gravity, and the copolymer can be easily produced.

In addition, the present invention was able to sufficiently solve the problem of poor dispersibility of finely divided inorganic substances in polymers, which generally exist in polymers with good particle shapes.

Films and sheets made from polymers obtained according to the present invention have extremely good performance and appearance, and can be used satisfactorily. This means that the specific surface area of the polymer particles obtained in the present invention is 0.31471 or more and 1.5 n? /
f or less, and its pore volume is 0.3 crl/
It is based on 1 or more and 1.5 cl/f or less.

Another major effect of the present invention is that even if the step of drying the solid product (n) and the step of prepolymerization in the earlier invention are omitted, the same effects as in the earlier invention can be obtained; By omitting the steps, the solid product (II) can be produced very easily.

The present invention will be explained below with reference to Examples.

In Examples and Comparative Examples, the definitions or measurement methods of various properties that define the polymer are as follows.

(1) Melt 7o-rate (abbreviated as Mpg) is AST
Based on MD1238(L).

(2) The bulk density of the polymer (BD, abbreviated as f') is AST
According to MD 1895.

(3) The shapes of the solid product (1), the solid product (It), and the polymer particles were observed using an optical microscope.

The polymers obtained in all Examples were spherical or nearly spherical.

(4) The particle size distribution of the polymer was determined according to JIS K 0069 using a sieve according to JIS Z 8801. Also,
The particle size distribution of solid product (1) and solid product (II) was measured using Microto 2 manufactured by Leeds & Northrup.
Measured using a Tsuku analyzer.

(5) The particle size of cumulative 50% by weight of the particle size cumulative curve in the above particle size distribution is the average particle size, and the value obtained by dividing the cumulative particle size of 85% by weight by the cumulative particle size of 15% by weight is the uniformity index. .

(6) The amount of polymer fine powder is the ratio of the amount of polymer having a particle size of less than 100 μm to the total amount.

(7) II In the case of liquid phase polymerization using an inert hydrocarbon: liquid phase polymerization using an α-olefin as a solvent and gas phase.

In the case of polymerization: (8) I I (2) means In the case of liquid phase polymerization using an inert hydrocarbon: In the case of liquid phase polymerization and gas phase polymerization using α-olefin as a solvent: (9) In the present invention The specific surface area of the obtained polymer particles is 0.2771'/9 or more and 2 i/f or less, preferably o, am"/f, when measured by a gas adsorption method.
is greater than or equal to 1.5 m/f. Moreover, the pore volume of the polymer particles is 0.0 when measured by mercury porosimetry.
1 cr/l/y or more 2 cr&/? Below, preferably 0.3 crl/9 or more 1.5 crl/f
It is as follows. In order to improve the dispersibility of silica gel, it is preferable that both of them be large, but if they are too large, the polymer particles become susceptible to attrition, so there is an upper limit.

The roughness of the product surface can be determined using a surface roughness tester, the transparency of the product can be determined using a haze measuring device, the fisheye of the product can be determined using a fisheye colorator, and the degree of spider 9 degree of the product can be determined using a sensory test using the naked eye.

Example 1 (1) Preparation of supported solid catalyst component In a glass flask, 30 d of purified decane, 4.76 fs of anhydrous magnesium chloride, 0.
47f, Louptil orthotitanate 17F, and 2-ethyl-1-hexanol 1942 were mixed and heated to 130° C. for 1 hour with stirring to dissolve and form a uniform solution. The solution was heated to 70°C, 3.22% of ethyl benzoate was added and reacted for 1 hour, and then 522% of silicon tetrachloride was added with stirring.
was added dropwise over 2 hours to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (1).

The total amount of the solid product (1) was converted into 1,2-dichloroethane 5
The mixture was mixed with 501 nl of titanium tetrachloride dissolved in 0.011 Lt and reacted at 80° C. for 2 hours with stirring, then washed with purified hexane, and purified hexane was added without drying to form a hexane suspension.

There were 501 solid products (■) in the suspension 11.

The above-mentioned operations and similar operations in subsequent Examples and Comparative Examples were all performed under a nitrogen atmosphere.

The solid product (■) was spherical, with an average particle size of 20 μm and a uniformity index of 1.29. 25℃, under reduced pressure (10”mx
Hg) The compositional analysis results of the solid product (...) obtained by drying for 3 hours were TI 3.8% by weight (hereinafter referred to as "CH"), CI
57.0chi, Mg17.6chi, AlO, 8chi, 8i0
．． 9th, ethyl benzoate 7.2%, butoxy group 2.
4 and 4.3 2-ethylhexanoxy groups.

(2) Production of polyolefin 1.5 mmol of triethylaluminum was placed in a stainless steel reactor with an internal volume of 31 cm and equipped with a multistage stirrer, which was purged with nitrogen.
and diethylaluminum chloride Q, 5mmo11p
- Methyl toluate 0.5 mmol.

After adding 4 x 10"m of Ti atoms and 500ml of hydrogen to the solid product (II), polymerization was carried out for 2 hours at 70°C while continuously introducing propylene so that the total pressure was 22kli'/ff1G. I did it.

Thereafter, unreacted propylene was discharged to obtain powdered polypropylene 1901. BD of the powdered polypropylene
is 0.45, MFR is 3.2, the polymer particles are spherical or nearly spherical, and the average particle size is 600 μm.
Index: 1.701 The amount of fine powder with a particle size of 100 μm or less was 0.02% by weight of the total. The residue extracted with boiling hexane [IX (1)] is 983, and the residue extracted with boiling hexane [IX (2),
) was 97.9%. The powdered polypropylene obtained after polymerization was not susceptible to milling.

(3) Physical properties test 0.09% by weight of antioxidant, 0.1% by weight of lubricant, and fine particulate silica gel (average particle size 3 μm) o, 4s heavy weight Ji[] were added to the polypropylene obtained in (2) of Example 1. The mixture was added and thoroughly mixed in a Henschel mixer, and granulated at 220°C to produce a sheet with a thickness of 25 μm at 240°C. The sheet surface is smooth and has no problems with transparency.
Fish eyes (particles with an average particle diameter of 0.15 mm or more) can be used without any problem at 20 pieces per 1000 cIl sheet.
The product had a good appearance. In addition, Example 1
The specific surface area of the polypropylene particles obtained in (2) is o
, 5s75/p, pore volume is o, s s cII/
It was y.

Comparative Example 1 In Example 1, the solid product (■) was washed with purified hexane and then heated at 25° C. under reduced pressure (10”ynmHg)3
A supported solid catalyst component was prepared in the same manner as in Example 1 except that the solid product (n) equivalent was obtained by drying for a period of time, and polyoleinine was produced using the solid product (II) equivalent.

Comparative Example 2 Solid product (I[) equivalent 3 obtained in Comparative Example 1
1 cooled to 0°C, 5 m of triethylaluminum
The polymer yield in the suspension was about 51.
-Polymer/f-2 ethylene to form a solid product
I took the time.

The filtrate was washed with purified hexane until triethylaluminum was no longer detected, and then heated at 25°C under reduced pressure (10” m
mHg) After drying for 3 hours, a solid product (III) was obtained. The Ti content in the solid product (1) was 0.60 Ti. Example 1 (2) except that the solid product (ill) is used in place of the solid product (n) in Example 1 (2).
A polyolefin was produced in the same manner.

Example 2 (Contents of 11 polyolefin !lI! Nitrogen purification) Purified hexane 11 was placed in an autoclave of 2 A!, and 2 ml of triethylaluminum was added.
rLol, 0.5 mmol of methyl p-toluate and the solid product (II) obtained in (1) of Example 1 were added to Ti
After adding 4X10 '■ atoms in terms of atoms and adding 300 g of hydrogen, the total pressure of propylene is 1 okg/Cr! G
1 at 70℃ while continuously introducing
Time polymerization was performed. Thereafter, the hexane insoluble matter was dried door to door to obtain powdered polypropylene 942. The powdered polypropylene had a BD of 0.44, an MFR of 2.7, a spherical polymer particle, an average particle size of 390 μm, a uniformity index of 1.40, and an amount of fine powder of 0.07% by weight. The residue extracted with boiling hebutane (II(2)) was 97.7%. On the other hand, the furnace solution after separating the hexane insolubles was evaporated to dryness to obtain 1.9 tons of solubles.

(2) Using the polypropylene obtained in physical property test (1), Example 1 (3)
) A film with a thickness of 25 μm was produced in the same manner. The product was sufficiently good. In addition, the specific surface area of polypropylene is 0°62 m/f, and the pore volume is 0.607
/t.

Examples 3 to 4 In Example 1 (11), 1
Using 251 for 770s (Example 3) or 32 instead of 2-ethyl-1-hexanol 19.4f
．． 3? Example 1 (1) except for using (Example 4)
Supported solid catalyst components were prepared in the same manner as in Example 1, and polyolefins were produced in the same manner as in Example 2, using these solid catalyst components in place of the solid product (n).

Example 5 In (1) of Example 1, aluminum chloride 047t
Instead of 2. A supported solid catalyst component was prepared in the same manner except that Or was used, and this solid catalyst component was converted into a solid product (
A polyolefin was produced in the same manner as in Example 2 except that the compound was used in place of If).

Example 6 A supported solid catalyst component was prepared and a polyolefin was produced in the same manner as in Example 1 except that 1.9 f of ethyl acetate was used in place of 1.9 f of ethyl benzoate.

Example 7 (1) Preparation of supported solid catalyst component In a stainless steel flask, purified nonane 50-1
Anhydrous magnesium chloride 4.76F, aluminum chloride 2
．． Or, ethyl orthotitanate 17, 15' and 13F of fluoro-octyl alcohol were mixed, and without stirring 10
The mixture was heated to 0° C. for 2 hours to dissolve and form a homogeneous solution. The solution was heated to 70°C, and ethyl silicon trichloride 571 containing 3,22 p-ethyl anisate was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to yield the solid product (I
) was obtained. The solid product (1) was mixed with 50ml of titanium tetrachloride dissolved in 50ml of toluene, reacted at 100°C for 1.5 hours with stirring, then washed with purified hexane, and without drying, purified hexane. was added to form a hexane suspension. The solid product (■
) existed 1Of.

The solid product (II) is spherical, with an average particle size of 23 μm1
The uniformity index was 1.33.

Solid product (It) obtained by drying under reduced pressure at room temperature for 3 hours
The composition analysis results are Ti 3.5%, Cl 58.4
%, Mg 18.1%, A11.1%, Si0.6%,
Ethyl anisate was 6.s%, ethoxy groups 1.9% and octanoxy groups 3.6%.

(2) Production of polyolefin In a nitrogen-substituted autoclave with an internal volume of 3.61 cm, 4.5 mmol of triethylaluminum, 1.5 mmol of ethylaluminum dichloride, 1.5 rnmol of methyl p-toluate, and a solid product (1 ( I
) was added with 8 x 10'' atoms in terms of Ti atoms, 500 ml of hydrogen was introduced into liquid propylene along with !9, and polymerization was carried out at 70°C for 1 hour. During this time, the total pressure was 32
kg/io. Thereafter, unreacted propylene was discharged to obtain powdered polypropylene 275F. The powdered polypropyref (DBD is 0.43.MF'R is 3.
01 The polymer particles have a spherical or nearly spherical shape,
The average particle size is 470 μm, the average index is 1.65, and the particle size is 1.
The amount of fine powder of 00 μm or less was 0.04% by weight of the total. The residue extracted with boiling hexane (I (11) is 9
7.8%, and the boiling hexane extraction residue (II (2)) of the hexane extraction residue was 97.7%.

Comparative Example 3 In Example 7, the solid product (It) was washed with purified hexane and then dried under reduced pressure at room temperature for 3 hours to obtain the solid product (It).
II) A supported solid catalyst component was prepared in the same manner as in Example 7 except that the equivalent was obtained, and a polyolefin was produced using the solid product (It) equivalent.

Comparative Example 4 Solid product (It) equivalent 3 obtained in Comparative Example 3
1 was suspended in 400 ml of purified hexane containing Iommol of triethylaluminum cooled to 5°C in an atmosphere of propylene, and the polymer yield in the suspension was about 101-polymer/2-1 at the same temperature with stirring. Propylene was bubbled in over 4 hours to give a solid product (n). The solid product (III) was obtained by washing with purified hexane and drying under reduced pressure at room temperature for 3 hours. The Ti content in the solid product (III) was 0.29%. The solid product (11[) was converted into the solid product (1) of Example 7 (2).
) A polyolefin was produced in the same manner as in Example 7 (2) except for using the following.

Example 8 In a glass flask, purified kerosene 30-1 anhydrous magnesium chloride 4.76 f, ethylaluminum dichloride 0.64 t, polytitanic acid looptyl (5
A mixture of 4.2 t and 7.72 t of ruhexyl alcohol was mixed and heated to 110° C. for 1.5 hours with stirring, and a trace amount of insoluble matter was removed in a furnace to obtain a homogeneous solution. The solution was heated to 60°C, and silicon trichloride 72F was added dropwise over 3 hours to precipitate a solid, which was further stirred for 1 hour, followed by methyl p-toluate 3. Ol was added and reacted at the same temperature for 1.5 hours. The solid was separated from the solution and washed with purified hexane to obtain a solid product (1). The solid product (1) is titanium tetrachloride 100+++A! After mixing with and reacting at 110°C for 2 hours with stirring and washing with purified hexane, a solid product (II) was prepared in the same manner as in Example 1. In Example 2, 2 mmol of triethylaluminum 1.5 m mol of triethylaluminum,! : A polyolefin was produced in the same manner as in Example 2, except that 0.5 mmol of ethylaluminum dichloride was used and the solid product (n) of this example was used in place of the solid product (II) of Example 2. The solid product (It) is spherical, and the composition analysis results of the solid product (II) obtained by drying under reduced pressure at room temperature for 5 hours are T13.6, A 0.9, and 8+0.5. , 6.0% methyl toluate, 2.3 butoxy groups and 3.5 hexanoxy groups.

Example 9 In Example 1, 1.9 t of ethyl benzoate was used instead of 3.2 f, silicon tetrachloride was added to precipitate a solid, and after further stirring for 1 hour, 1.5 f of ethyl benzoate was used.
A supported solid catalyst component was prepared and a polyolefin was produced in the same manner as in Example 1, except for adding and reacting for 1 hour.

Example 10 In Example 7, instead of dropping ethyl silicon trichloride containing 3.02 t of p-ethyl anisate, ethyl silicon trichloride containing 1.6 t of p-ethyl anisate was dropped to precipitate a solid. After further stirring for 1 hour, ethyl P-anisate 1
．． A supported solid catalyst component was prepared and a polyolefin was produced in the same manner as in Example 7 except that 41F was added and reacted.

Example 11 A polyolefin was produced in the same manner as in (2) of Example 1, except that propylene containing 1 Q mol % of ethylene was used instead of propylene in (2) of Example 1, and powdered propylene- An ethylene copolymer was obtained. The ethylene content in the copolymer was 6.8 mol%.

Antioxidant 0.1 was added to the polypropylene obtained in this example.
% by weight, 0.1% by weight of a lubricant, and 4% by weight of finely divided silica gel (average particle size 3 μm) were added, thoroughly mixed in a Henschel mixer, and granulated at 220°C.
A film with a thickness of 30 μm was produced at 0°C. The film surface is smooth and reedy, there are no problems with transparency or cloudiness, and there are 16 fish eyes (particles with an average particle size of 0.15 ram or more) per 100 o7 of film.
The product had a satisfactory appearance.

The specific surface area of the polypropylene particles obtained in this example was 0.37111/f, and the pore volume was 0.44c.
It was rl/l.

Example 12 In Example 2, instead of solid product (n), Example 9
A polyolefin was produced in the same manner as in Example 2 except that the solid product (II) obtained in Example 2 was used and propylene containing 10 mo1% of 1-butene was used instead of propylene. A butene copolymer was obtained. The butene content in the copolymer is 3. f3mo was 1%.

Example 13 In (1) of Example 1, aluminum chloride 0, 47
Diethyl aluminum chloride 0.422 in place of 9
After preparing a homogeneous solution using a hexane solution 4- containing f, ethyl benzoate 1.
58 f was added and reacted for 1 hour, followed by silicon tetrachloride 5
21 was added dropwise over 2.5 hours to precipitate a solid, followed by stirring at 70° C. for 1 hour. Furthermore, ethyl benzoate 2,1
1 was added thereto and reacted at 70°GK for 1 hour, after which the solid was separated and washed with purified hexane to obtain a solid product (1).

Thereafter, the same procedure as in Example 1 (11) was carried out to obtain a solid product (n
) was prepared, and polypropylene was produced in the same manner as in Example 2 using this solid product (■).

Comparative Example 5 After washing the solid product (II) with hexane in Example 1, the solid product (n) was dissolved in purified hexane 2ON.
A hexane suspension exists in a ratio of 1 to 1, and the suspension is
After drying for 1 hour in a stream of purified nitrogen while maintaining the temperature at 0° C., a solid product (n) containing 20% by weight of hexane was obtained in the form of a powder. The solid product containing hexane (II
) was used in place of the solid product (If) in (2) of Example 1, but a polyolefin was produced in the same manner as in Example 1.

The results are shown in the table.

Example 14 Solid product (1) was reacted with titanium tetrachloride in dichloroethane in the same manner as in Example 1 (11), and after washing with purified hexane, hexane and solid product (n) were in the same weight ratio. The solid product (II) was used to produce a polyolefin in the same manner as in Example 1 (2).The results are shown in the table.

Procedural amendment document September 1985 Zz 1, Indication of the case 1982 Patent Application No. 25.480 2, Name of the invention Method for manufacturing a catalyst component for polyolefin production 3, Person making the amendment and the case Related Patent applicant: 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(207) Chisso Corporation representative Sadao Nogi 4, agent 6, number of inventions not increased due to amendment 7, claims of the specification to be amended and detailed description of the invention.

8. Contents of amendment Correct the statement as follows.

A. Correct the entire text of the claims as shown in the attached sheet.

B1 The detailed description of the invention is amended as follows.

(1) Page 10, line 12 (7) r R3+ 0-Ti
(R') (R5) r R3-f 0-
Ti(OR') (O115) bo-R' J 2 corrections.

(2) 3rd line from the bottom of page 17 and 5th line from the bottom of page 21
Insert "Used" after "Amount used" in the first line.

(3) Page 30, lO-11th line r Q, 3 m'/g or more and 1.5 m'/g or less'' is rO,! 5 or more Jz 1. O
rn'/g or less.''

(4) r Q on the 2nd line of I on the same page, 3m'/g or more 1.5
rrf/g or less J is ro', 15 or more 1.0rn'/g
The following is corrected.

(5) On page 33, lines 1 and 2, "r 0.2rrf/g or more and 2m'/g or less" is corrected to "ro, 15 or more and 1.0m'/g or less".

(6) r on the 2nd to 3rd lines of the same page 0.3 m'/g or more 1.
5rn'/g' is corrected to '0.2 or more and 0.7rn'/g or less.'

(7) On the 4th line of the same page, before "pore volume", "pore diameter 0.
003p-m or more and less than 1071m" is inserted.

(8) ro on the 4th to 5th lines of the same page, 1crrf/g or more 2c
rn″/g or less” is rO, +5 or more 1.0crrf/g
The following is corrected.

(9) Same page lines 5-6 ['' rQ, 3crn'/g or more 1
．． 5 cm'/g or less" to "0.2 or more 0.7 cm'/g
The following is corrected.

(lO) r 0.55J on page 36, line 14, r 0
．． 23J, r 0.58J is corrected to r Q, 24J, respectively.

(11) M 38JT lower collar 2nd row (7) rO, 8
2J Wolo, 211tJ, r O, 8 on the last line of the same page
Correct 0J to r O and 25J, respectively.

(12) r 0.3 on page 48, line 8? J r 0.2
0J and r 0.44J to r O, 22J, respectively.

9. Attachment Attached sheet (full text of claims) 1. Attachment 2 (full text of claims) (+) (, L) Anhydrous magnesium cybaride, aluminum halide column, titanate ester and (2) Mixing and dissolving alcohol in an inert hydrocarbon solvent; (2) reacting a silicon halide and an organic acid ester with the thus obtained solution to precipitate a solid product (1); (2) producing the solid product; (2) The solid after the reaction is washed with a liquid inert hydrocarbon to obtain a solid product (II);
) in the coexistence of at least 50% by weight of a liquid inert hydrocarbon.

(2)■Aluminum halide has the general formula AIX+1
%-n (here, -t-x is C1 or Br, R' is an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aryl group having 3 to 10 carbon atoms)
1O cycloalkyl group, n is a number from 0 to 3), and the titanate ester is an orthotitanate ester represented by the general formula Ti(OR2)a or a compound with the general formula n3
-TiU■Y-αSugo) B2. Ra, H4, R5 and R6 are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to IO carbon atoms, m is 2 to 2
0), (7i) the alcohol is an aliphatic saturated or unsaturated alcohol having 1 to 20 carbon atoms; The titanate ester of
0.5mol, 0.5~1.5mol and 0.5~
Using 5 mol, φ) In an inert hydrocarbon solvent, anhydrous magnesium cybaride, aluminum halide from (1) above, titanate ester from (2) above, and alcohol from (2) above were heated at 50 to 150°C.
, O to 5 kg/cm'G for 10 minutes to 5 hours to dissolve by stirring or shaking.

(3)■ Silicon halide has the general formula 5iXonS-*
or 5iXp (OR' )4-p (here-c'
x is CI or Br, and R' and B11 are each an alkyl group having 1 to IO carbon atoms.

an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, or p is a number of 1 to 4), and the organic acid ester is an aliphatic or aromatic ester having 2 to 20 carbon atoms. ■Inert hydrocarbon solution of anhydrous magnesium cybaride, aluminum halide, titanate ester, and alcohol, 1 m of magnesium cybaride
01, using 1 to 20 mol of (organic) silicon halide and 0.1 to O,f (mol of organic acid ester) +4) + 50 to 130°C for the solution of
, θ ~ 5 kg/crtfG for 10 minutes ~ 5 hours, (organic)
A method according to claim 1, in which a silicon halide and an organic acid ester are mixed to precipitate a solid product (I).

(4) To an inert hydrocarbon solvent solution of anhydrous magnesium cybaride, aluminum halide, titanate ester, and alcohol, (■organic acid ester and silicon halide are mixed together, or (■organic acid ester and By simultaneously mixing the silicon halide, or (2) mixing the silicon halide and then mixing the organic acid ester, or (2) using a part of the organic acid ester and or silicon halide, any of the above After carrying out the mixing reaction of (b), the remaining organic acid ester and/or silicon halide are mixed by any one of methods (1) to (3) other than the first step (a). Method described.

(5) ■ Wash the solid product (1) with an inert hydrocarbon solvent, and add the general formula TiXq (OR' )4-q (Cocote
4fc1. I+9 c) ie an alkyl group with a prime number of 1 to 10,
An aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and q is 1 to 4. , using 3 to 50 m'o l of titanium halide in the above (■),
The method according to claim 1, wherein the reaction is carried out at 130 DEG C. and O.about.5 kg/crn'G for 10 minutes to 2 hours, and (2) the thus obtained solid product (II) is used.

Procedural amendments Manabu Shiga, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 25.480 of 1982, Title of the invention, Process for producing a catalyst component for polyolefin production3, Person making the amendment, Relationship to the case Patent Applicant: 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(2'07) Chisso Corporation Representative Sadao Nogi 4, Agent 2-8-1 Shinjuku, Shinjuku-ku, Tokyo (160) 6, No number of inventions increased by amendment 7, Specification subject to amendment Column for detailed description of the invention.

8. Contents of amendment Correct the statement as follows.

r□ on page 30, line 12, 3cm'/g or more 1.5cm
'/g or less' is ro, 15 or more 1. Qcm'/g or less"
Correct.

that's all

Claims (1)

[Scope of Claims] (1) ■ Anhydrous magnesium cybaride, aluminum halide, titanate ester, and alcohol are mixed and dissolved in an inert hydrocarbon solvent, ■ Silicon halide and organic Mixing the acid esters to precipitate a solid product (1), (1) reacting the solid product with titanium halide and/or vanadium halide, and (2) reacting the solid after the nuclear reaction with liquid inert hydrocarbon. A catalyst component for polyolefin production, characterized in that the solid product (II) is obtained in the coexistence of at least 50% by weight of a liquid inert hydrocarbon. How to manufacture. (21) Aluminum halide has the general formula AIXnB'5-n (where X is C6 or Br+R' is an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and R is O The titanate ester is an orthotitanate ester represented by the general formula T i (OR) or the general 2R'-f-0-Ti (R'Xl
'L'')-Clam 0-Polytitanate ester represented by R6 (where 几2, BS, B4, Rm and 几6 are an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms) group, m is a number from 2 to 20), (1) the alcohol is an aliphatic saturated or unsaturated alcohol having 1 to 20 carbon atoms, (2) halogenation of the above (2) to anhydrous magnesium cybaride lnLol Aluminum, the titanate ester of the above (2), and the alcohol of the above (2), each at 0.01
Using ~0.5 mat, 0.5-1.5 nol and 0.5-5rILOl, (1) anhydrous magnesium cybaride in an inert hydrocarbon solvent, aluminum halide (2) above, titanate ester (2) and Said■
of alcohol at 50~150℃, θ~5 kg/ly!
The method according to item (1) above, wherein the method is dissolved by stirring or shaking with G for 10 minutes to 5 hours. (3) ■ Silicon halide has the general formula 8iXlR', or 5txp(oa")
4-p (where X is C1 or Br, 几7 and R8
are each an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and l or p is a number of 1 to 4); an aliphatic or aromatic carboxylic acid ester having 2 to 20 carbon atoms; ■ anhydrous magnesium di/S-ride in an inert hydrocarbon solvent solution of anhydrous magnesium dino-ride, aluminum titanate, and alcohol;
mol, using 1 to 20 mol of (organic) no-loginated silicon and 0.1 to Q, f, not organic acid ester, ~5k
g/CIIG for 10 minutes to 5 hours to form a solid product (1) by mixing the (organic) silicon halide and the organic acid ester.
A method according to claim (1) for precipitating. (4) For solutions of anhydrous magnesium dino)lide, aluminum chloride, titanate ester, and alcohol in an inert hydrocarbon solvent. ■ Mix the organic acid ester and then mix the silicon halogenide, or ■ Mix the organic acid ester and the silicon halogenide simultaneously, or ■ Mix the silicon halide and then mix the organic acid ester, or ■ The organic acid ester and the silicon halogenide. A part of the acid ester and/or silicon halide is used to carry out the mixed reaction of any one of (1) to (2) above, and the remaining organic acid ester and/or silicon halide is used to carry out the reaction (2) other than the first step (a). The method according to claim (3), wherein the mixing is performed by any of the methods described in (1) to (3). (5) ■ Wash the solid product (1) with an inert hydrocarbon solvent, ■ Add to the purified product of ■ above as a titanium halide with the general formula 'i'r (X is Cl, 9 is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, hD is hD, and q is 1 to 4). For an amount equivalent to 1 mol of anhydrous magnesium cybaride in product (1), use the titanium halide described in (1) above at a concentration of 3 to 5 degrees, and (2) react at 50 to 130°C and θ to 5 kg/cIItG for 10 minutes to 2 hours. 2. The method according to claim 1, wherein the solid product (It) thus obtained is used.