JPS60192709A - 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 obtained by dissolving, by heating, 1mol of a Mg alkoxide (e.g., Mg diethoxide), 0.001-0.7mol of an Al halide (e.g., AlCl3), 0.1- 3mol of a titanate ester (e.g., orthotitanate), 0.1-6mol of an alcohol (e.g., n- hexyl alcohol) and, optionally, 0.05-0.5mol of an organic acid ester (e.g., ethyl acetate) in an inert hydrocarbon solvent is mixed and reacted with 0.1-50mol of a Si halide (e.g., SiCl4) and 0.05-0.6mol of an organic acid ester 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 an 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, 1. The present invention uses 8° magnesium alkoxide, aluminum halide, titanate ester,
Alcohol and optionally organic acid ester (I), or b.

Magnesium alkoxide, aluminum halide, and organic acid ester (I) are co-pulverized to form a complex compound, and the complex compound titanate ester and alcohol are heated and dissolved in an inert hydrocarbon solvent for each of the above a and b. The present invention relates to a method using a solid product (I) precipitated by subjecting a solution obtained to a mixed reaction of a silicon halide and an organic acid ester.

However, in the present invention, polyolefin refers to a homopolymer of α-olefin having 3 or more carbon atoms and a polyolefin having 3 or more carbon atoms.
A copolymer of the above α-olefin and another α-olefin having 2 or more carbon atoms, in which the proportion of the former component in the copolymer is 50% by weight or more.

Conventionally, the directions for improving Ziegler-Natsuta type catalysts are as follows:
Catalysts that have high polymerization activity and can produce polymers with high stereoregularity have been energetically pursued. However, in recent years, in addition to these performances, there has been a demand for the performance that the resulting polymer has a good particle shape.

The inventors, including the present inventor, have already filed a patent application in 1983 for a method for producing polyolefins using a supported solid catalyst component that provides polymers with high polymerization activity, high stereoregularity, and good particle shape. -189012 (hereinafter referred to as the prior invention). This proposal differs from the present invention in that after obtaining a solid product (II) from magnesium alkosites in the same manner as the present invention, the solid product (II) is dried to the extent that almost no liquid inert hydrocarbon remains. This is a method for producing a polyolefin by preparing a solid powder and then prepolymerizing it to obtain a supported solid catalyst component, and using the supported solid catalyst component. However, as a result of intensive studies aimed at simplifying the manufacturing process of the supported solid catalyst component, it was discovered that the two steps of drying the solid product (II) and prepolymerization of the earlier invention could be omitted. This led to the present invention.

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

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

(1) Cj') a, -7 Cnesium alkoxide, aluminum halide, titanate ester, alcohol and, if necessary, organic acid ester (I) are dissolved by heating in an inert hydrocarbon solvent, or silver, magnesium The alkoxide, aluminum halide, and organic acid ester (I) are co-pulverized to form a complex compound, and the complex compound, titanate ester, and alcohol are heated and dissolved in an inert hydrocarbon solvent. The resulting solution is reacted with silicon halide and organic acid ester (II) to form a solid product (I).
(♀) Titanium halide and/or are added to the solid product (I).
Or react with vanadium halide.

(4) The reaction? The solid of M is washed with a liquid inert hydrocarbon to give a solid product (II);
A method for producing a catalyst component for polyolefin production, characterized in that II) is obtained in the coexistence of at least 50% by weight of a liquid inert hydrocarbon.

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

First, a method for manufacturing a supported solid catalyst component supporting a transition metal compound will be described.

First, magnesium alkoxide is mixed with (a) aluminum halide, titanate, and alcohol in an inert hydrocarbon solvent, and optionally an organic acid ester, and dissolved by heating, or (b).

Magnesium alkoxide, aluminum halide, and organic acid ester are co-pulverized to form a complex compound, and this complex compound is heated and dissolved in an inert hydrocarbon solvent in the coexistence of titanate ester and alcohol.

Magnesium alkoxide is generally a compound represented by Mg(OR')2, where RO has 1 to 15 carbon atoms.
represents an alkyl group, an aryl group, a cycloalkyl group having 3 to 15 carbon atoms, an aralkyl group, etc. Examples include magnesium dimethoxide, magnesium jetoxide, magnesium diproboxide, magnesium diptoxide, magnesium dicyclohexoxide, magnesium alkoxide, and magnesium diphenoxide. The aluminum halide is a compound represented by AIX*R%-n, where X is C1 or Or, and R' is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms. The group n is a number from O to 3. Examples include aluminum trichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, dipropylaluminum chloride, aluminum tribromide, ethylaluminum dichloride, and the like. As the titanate ester, ol-I represented by Ti(O12)4 is used.
Titanate ester and rl' + OTi (rl'
)(R5)b Polytitanate ester represented by Orl'. Kokote, R2,n'', It', R
5oJ: and R6 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 a number from 2 to 20. Specifically, methyl orthotitanate.

Ethyl orthotitanate, n-propyl orthotitanate,
Orthotitanate esters such as n-butyl orthotitanate, $i-amyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, Polytitanic acid n-butyl, polytitanic acid! Polytitanate esters (2 to 20 types) such as -butyl, n-amyl polytitanate, phenyl polytitanate, and cyclopentyl polytitanate can be used. Alcohol has 1 to 1 carbon atoms
8 aliphatic alcohols and/or aromatic alcohols having 6 to 24 carbon atoms can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, and i-7 methyl alcohol.

n-hexyl alcohol, n-heptyl alcohol.

In addition to monohydric alcohols such as n-octyl alcohol, 2-ethyl-1-hexyl alcohol, and benzyl alcohol, ethylene glycol, trimethylene glycol,
Polyhydric alcohols such as glycerin can also be used. Among these, aliphatic alcohols having 4 to 10 carbon atoms are preferred. Phenols such as phenol or its derivatives can also be used in place of or in conjunction with these aliphatic alcohols. Inert hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, benzene,
Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane and chlorobenzene can be used. Among these, aliphatic hydrocarbons and halogenated aliphatic hydrocarbons are preferred.

Organic acid esters (41 organic acid esters used in this step are referred to as organic acid esters (I)) include ethyl ethyl, propyl acetate, butyl acetate, propionbutyethyl,
2 or more carbon atoms such as butyl propionate and ethyl intoxicant
18 aliphatic carboxylic acid esters, or aromatic carboxylic acid esters having 8 to 24 carbon atoms, such as methyl benzoate, AnQ, ethyl fragrant, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate. .
, As a method for specifically dissolving magnesium alkoxide, in the method ① described above, ②a, magnesium alkoxide, /\aluminum halogenide, titanate ester, and alcohol are added in any order in an inert hydrocarbon groove agent. The aluminum halide, titanate ester, and alcohol are heated with stirring in an inert hydrocarbon groove agent, and magnesium is added to the solution. Add alkoxide and dissolve. Alternatively, a method may be used in which magnesium alkoxide, titanate, and alcohol are heated and dissolved in an inert hydrocarbon solvent, and aluminum halide is added to the solution. In either method, the organic acid ester (I) can be added at any stage. The purpose of adding the organic acid ester is to make the dissolution of the magnesium alkoxide smooth and uniform, and to improve the stereoregularity, and to that extent it is essential.

As a method for dissolving magnesium alkoxide using the method described above (Db), first, the three components are reacted to form a complex compound using methods 1 to 2 below.

That is, (1) magnesium alkoxide, aluminum halide, and organic acid ester are simultaneously mixed and subjected to a pulverization reaction (hereinafter referred to as co-pulverization). (b) Co-pulverizing the mixture or complex of aluminum halide and organic acid ester and magnesium alkoxide. ■ Add aluminum halide to the mixture or complex of magnesium alkoxide and organic acid ester and co-pulverize. Alternatively, 41-acid ester may be added to a mixture or co-pulverized product of magnesium alkoxide and aluminum halide and co-pulverized, and any method may be employed. Among these, methods ①, ②) or ①) are preferred. These reactions can be accomplished by means of co-milling (described above). A vibrating mill is used as a means of co-grinding.

A ball mill, a vibrating ball mill, or the like is used.

Magnesium alkoxide is thought to undergo a complex reaction upon contact with aluminum halide and organic acid ester. During co-grinding, fatty hydrocarbons such as hexane, heptane, nonane, decane, and kerosene, aromatic hydrocarbons such as benzene, toluene, and xylene, or carbon tetrachloride, 2-dical ethane, n-butane chloride, and chloro Halogenated hydrocarbons such as benzene may also be used.

When these solvents are used, the solvents may be separated by filtration after co-pulverization, or may be used as they are for the next reaction. In addition,
It is known that aluminum halides and organic acid esters and magnesium alkoxides and organic acid esters form complexes, and these complexes or mixtures may be used for co-pulverization. These complexes can be made by co-milling or reaction in solution. As the solvent for such solution reaction, the same solvent as that for co-pulverization described above can be used.

A complex compound composed of magnesium alkoxide, aluminum halide, and organic acid ester is obtained by powdering at room temperature, but it can be easily dissolved in hydrocarbons in the next step, that is, in the coexistence of titanate ester and alcohol. In order to achieve this, the powder of the complex compound is preferably a fine powder having as large a specific surface area as possible. The amount of aluminum halide used is 1 m of magnesium alkoxide.
0.001 to 0.7 mol, preferably 0
．． 01"0.5m01, 41 organic acid ester (I)
The amount used is 0.0% per 1 mol of magnesium alkoxide. (15 to 0.5 m01.

The amount of organic acid ester (I) to be used with respect to aluminum halide is 0.1 to 50 mol, preferably 0.5 to 10 mol, per 1 mol of aluminum halide. When using a solvent during co-grinding, the amount of solvent used is 0, (15-100ml) relative to the total amount log of magnesium alkoxide, aluminum halide, and organic acid ester used.
．． 67, preferably 0.1 to 50 van.

Aluminum halide and organic acid esthetics Jl/(I
) or when using a complex of magnesium alkoxide and organic acid ester (I), the complex may be created within the molar ratio range described above.

The co-milling temperature is θ~15 (1”U, preferably 20~1
5 hours at 0°C ranges from 5 minutes to 100 hours, but the time varies depending on the means of pulverization. For example, in a crushing method that can apply strong energy in a short period of time, such as a vibrating mill,
Minutes to 20 hours is sufficient, but grinding methods such as ball mills that require strong energy in a short period of time require 30 minutes to 10 hours.
Requires 0 hours. In co-pulverization, since the magnesium alkoxide is a solid and in some cases the aluminum halide is also a solid, the specific surface area should be adjusted to make it as homogeneous as possible and to facilitate the next operation as mentioned above. It is preferable to form a fine powder with a large size.

The complex compound obtained as described above is dissolved in an inert hydrocarbon solvent in the coexistence of a titanate ester and an alcohol.

Specific dissolution methods include: ■ Mixing the complex compound, titanate ester, alcohol, and inert hydrocarbon at the same time and dissolving them by heating; ■ Mixing the complex compound, alcohol, and inert hydrocarbon, and dissolving them before heating or After heating, titanate ester is added and heated to dissolve. ■ Mix the complex compound, titanate ester, and inert hydrocarbon, add alcohol before or after heating, and heat to dissolve; or ■ Mix the titanate ester, alcohol, and inert hydrocarbon, and before heating Alternatively, the complex compound may be added after heating and dissolved by heating, and any of the dissolution methods can be employed. Among these, these are preferred. Regardless of which method is used, the solids in the mixture may be completely dissolved to form a homogeneous solution;
A small amount of insoluble matter may remain. This insoluble material is believed to be due to impurities contained in the starting materials, such as magnesium alkoxide or aluminum halide. If a small amount of insoluble matter remains, it may have an adverse effect on the particle shape of the solid catalyst, so it is preferable to completely dissolve it to form a homogeneous solution. Alternatively, such a small amount of insoluble matter may be filtered off to form a homogeneous solution.

Heating is necessary to dissolve the aforementioned mixture. The temperature is 40-170℃, preferably 50-15℃
It is 0°C. The time is 5 minutes to 6 hours, preferably 10 minutes to 4 hours. If the organic acid ester contained in the complex compound is heated to a high temperature for a long period of time, it will change to other substances other than the organic acid ester and lose its ability to increase stereoregularity, so a high temperature is used when dissolving it. In such cases, it is necessary to take measures such as shortening the time. It is preferable that the temperature be as low as possible and the time be as short as possible. Therefore, it is preferable to filter out a small amount of insoluble matter that does not dissolve easily.

The amount of titanium acid ester to be used may be determined based on the amount of magnesium alkoxide contained in the magnesium alkoxide or complex compound. When orthotitanate is used as the titanate, polytitanic acid is used in an amount of 0.1 to 2.0 mol, preferably 0.5 to 1.5 mol, per mol of magnesium alkoxide in the magnesium alkoxide or complex compound. When using an ester, the molar ratio may be determined in the same manner as for the orthotitanate by converting the unit equivalent to the orthotitanate in the polytitanate molecule into a mol unit. The amount of alcohol used is magnesium alkoxy i'1m in magnesium alkoxide or complex compound.

0.1-6 mo+ for 1, preferably 0.5-5I
Il.

It is 1.

Use of titanate esters and alcohols 111. The greater the amount of halogenated silicon relative to the magnesium alkoxide, the greater the solubility of the magnesium alkoxide or magnesium alkoxide complex in an inert hydrocarbon solvent. However, an extremely large amount of silicon halide must be used for resolidification, and The transformation itself becomes difficult,
Even if solidification is possible, controlling the particle shape is extremely difficult.

On the other hand, if the amount of titanate ester and alcohol used is too small, the magnesium alkoxide or the magnesium alkoxide complex will not be soluble in the inert hydrocarbon solvent, and the solid catalyst will become amorphous, making it difficult to achieve the object of the present invention. I can't.

Furthermore, it is necessary to use both the titanate ester and the alcohol, and the purpose of the present invention cannot be achieved if each is used alone.

The amount of inert hydrocarbon used is 10 to 2000 ml, preferably 50 to 50 hl, per 10 g of the magnesium alkoxide complex compound. The composition of the compounds dissolved and present in solution is not clear.

Next, add silicon halide and organic acid ester (
II) is reacted to obtain a solid product (I). The method for obtaining the solid product (I) is as follows: (1) Add an organic acid ester to a solution containing magnesium alkoxide and react, and then add silicon halide to precipitate a solid; (2) Add silicon halide together with the organic acid ester. to react,
A solid can be obtained by any of the following methods: precipitating a solid; (2) adding silicon halide to precipitate a solid; then adding an organic acid ester and reacting; or a combination of two or more of these methods. Wash the obtained solid with an inert solvent
Mention may be made of methods for obtaining L solid product (I).

As the organic acid ester (II) used in this step, the aforementioned aliphatic carboxylic esters or aromatic carboxylic esters can be used.

As the silicon halide, compounds represented by the general formula siX, 1 part-0 and/or the general formula S+Xn (on8)4-TI can be used. Here, X is C1
or Br, rl' and C8 are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 1 to 10 carbon atoms, and n is a number of 1 to 4. Specifically, 5
iXn n'4-n, silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon pentachloride, cyclohexyl silicon trichloride, ethyl silicon tribromide, dichloride Diethyl silicon, dibutyl silicon chloride, triethyl silicon chloride, etc. can be used, SiX, (OR8
) 4-TI includes silicon tetrabromide, silicon trichloride, propoxy silicon trichloride, butoxy silicon trichloride, and phenoxy silicon trichloride.

Ethoxysilicon tribromide, jetoxysilicon dichloride, dibutoxysilicon dichloride, triethoxysilicon, and the like can be used. The above-mentioned compounds can also be used in combination of two or more. Among them, silicon tetrachloride is preferred. The organic acid ester (H) and the silicon halide may be used directly or diluted with a solvent.

In this case, the same solvent as the inert hydrocarbon solvent mentioned above can be used. The organic acid ester (11) is preferably added to a homogeneous solution and reacted with the silicon halide, either separately or simultaneously with the silicon halide. At this time, silicon halide may be added to the homogeneous solution,
The amount of the six organic acid esters whose homogeneous solution may be added to the silicon halide is 0.05 to 0.8 mol per mol of the magnesium alkoxide initially used. This Wk organic acid ester may be used all at once, or may be used in several stages. The reaction temperature is 30~
The temperature is 150°C, preferably 50 to 130°C, and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours per step. Organic acid ester (I) and organic acid ester (r
The total amount of r) used is 0 per mol of magnesium alkoxide used in the production of solid product (I).
．． 1 to 0.7 mol, preferably 0.1 to 0.8 m
It is ol. The reaction conditions for the homogeneous solution and silicon halide are a temperature of 40 to 150'O, preferably 50 to 130'O.
1 hour lul+ is 5 minutes to 10 hours, preferably 10 minutes to 5 hours
It's time. The amount of silicon halide used is 0.1 to 5 to 1 mol of magnesium alkoxy used.
oαal, preferably 1 to 20 mo I. A solid is precipitated by reacting the silicon halide. Since the particle shape of the Kokutai product (11) obtained in the next step is controlled by the particle shape of the solid product (I), the particle shape can be controlled by combining a homogeneous solution for precipitating the solid and silicon halide. Reaction is extremely important.

- After reacting an organic acid ester and a silicon halide in a homogeneous solution to precipitate a solid as described above, the precipitated reaction mixture is subsequently treated with anti-f8, that is, a titanium halide and/or a halide. A reaction with vanadium can also be carried out. However, it is preferable to wash the precipitated solid with the above-mentioned inert hydrocarbon. This is because unreacted substances or by-products present in the reaction mixture after the precipitation may hinder subsequent reactions. After separating and washing the precipitated solid from the reaction mixture, a solid product (1) is obtained.
is obtained.

Next, the solid product (I) is reacted with a titanium halide and/or a vanadium halide to obtain a IIJJ product (1). As titanium halide, TiXq (
[0119] Compounds represented by a-q can be used. Here, X is CI, C9 is an alkyl group having 1 to 1 degrees of carbon atoms, an aryl group, or a cycloalkyl group having 3 to 1 degrees of carbon atoms, and q is a number of 1 to 4. Specific examples include titanium tetrachloride, ethoxytitanium trichloride, propoxytane trichloride, butoxytitanium trichloride, octanoxytitanium trichloride, phenoxytitanium trichloride, and cyclohexoxytitanium trichloride.

Examples include jetoxytitanium dichloride, dibutoxytitanium dichloride, diphnynotitanium dichloride, triethoxytitanium chloride, and triphenoxytitanium chloride.

The above-mentioned titanium halides other than titanium tetrachloride can be produced by the reaction of titanium tetrachloride and orthotitanate, but a mixture of titanium tetrachloride and orthotitanate can also be used in this reaction. . As the orthotitanate, the same orthotitanate mentioned above can be used.

Vanadium halides include vanadium tetrachloride 11,
At least 1 vanadium oxytrichloride or chloro
Mention may be made of other vanadium derivatives that are present. Again, a mixture or reactant of vanadium tetrachloride or vanadium oxytrichloride and orthotitanate can be used in this reaction. Among these halides, titanium tetrachloride is most preferred. Titanium halide and/or vanadium halide can be used as is or diluted with a solvent.

The solvent in this case may be the same as the inert hydrocarbon solvent described above. The reaction of solid product (I) with titanium halide and/or vanadium halide is carried out by adding titanium halide and/or vanadium halide to a suspension of solid product (I) in the above-mentioned inert hydrocarbon. Alternatively, the solid product (I) may be added to the titanium halide and/or vanadium halide and reacted. The amount of titanium halide or vanadium halide used is 1 m of magnesium alkoxide used.
l-100 ■ O1 for o l, preferably 3-50
It is mol.

The reaction temperature of solid product (I) and titanium halide or vanadium halide is 40 to 150°C, preferably 5°C.
One hour at 0 to 130°C is 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

After the reaction, wash by filtration or decantation,
Remove unreacted substances or by-products. The solvent used during cleaning is a liquid inert hydrocarbon. Specific examples include aliphatic hydrocarbons such as hexane, heptane, nonane, decane, and kerosene. During and after the washing, it is necessary that the solid product (II) is in the presence of at least 50% by weight of the liquid inert hydrocarbon mentioned above. In particular, a decantation method is preferable for washing, and after washing, it is preferable that the liquid inert hydrocarbon coexists with the solid product (II) at least to the extent that the solid product (II) is immersed in the liquid inert hydrocarbon. . If only 50% by weight of liquid inert hydrocarbon is present with respect to the solid product (II), sufficient catalytic performance will not be exhibited even if this is subsequently combined with an organoaluminum compound and subjected to polymerization. That is, the polymer yield and bulk specific gravity are low, the shape is poor, the amount of fine powder φ is large, and the practicality is low.

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 (II) can be used as a catalyst for producing polyolefins by combining it with an organoaluminum compound and, if necessary, an organic acid ester as a solid catalyst component. As the organic aluminum compound, a compound represented by the general formula AlX5n1-s can be used. Here, X is C1, R'' is an alkyl group having 91 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and S is a number of O to 2. Triethylaluminum, tri-n-propylaluminum , Treaty butyl aluminum, Tricyclopentyl aluminum, Tricyclohexyl aluminum, Dimethyl aluminum chloride, Diethylaluminum chloride, Di-
Mention may be made of n-butylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and the like. Among them, triethylaluminum alone or a mixture of two types of 4741 aluminum compounds such as triethylaluminum and streamy butylaluminum, triethylaluminum and diethylaluminum chloride, and triethylaluminum and ethylaluminum sesquichloride, or triethylaluminum and streamy butylaluminum and ethylaluminum Mixed use of three organoaluminum compounds such as sesquichloride is also a preferred method of use.

As the organic acid ester, the organic acid ester (1) mentioned above is used.
Alternatively, the same compound as (II) can be used. Among them, aromatic carboxylic acid esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate are preferred.

The method of combining the solid product (II), the organoaluminum compound, and the organic acid ester is as follows: ■Solid product/product (II)
, feeding the organic aluminum compound and the organic acid ester independently to the polymerization vessel, ■ feeding the mixture of the organic aluminum compound and organic acid ester and the solid product (II) to the polymerization vessel independently, ■ solid product (11) , supplying a mixture of an organic aluminum compound and an organic acid ester to a polymerization vessel, and any of these methods can be adopted.

■ or ■ may be preferable in some cases. When combining the champions as described above, each component or any one of the components can be used after being 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℃.
, preferably -30 to +30°C, and the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is 1 mo of titanium atom contained in the solid product (II) as a solid catalyst component.
10 to 100100 O, preferably 50 to 5
00 mol. The amount of organic acid ester used is 0.01-1 mo per 1 mo I of organoaluminum compound.
1. Preferably it is 0.05-Q, 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.

Using a catalyst obtained by a combination of solid product (II) as a solid catalyst component, an organoaluminum compound, and an organic acid ester, an α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms. α-olefins having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1
, 4-methylpentene=1 and 3-methylpentene-
1 etc. can be used. In the polymerization of these α-olefins, not only homopolymerization but also other
It also includes copolymerization with one or more of the above α-olefins. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-pentadiene, etc. in addition to double α-olefins having 3 or more carbon atoms.

The amount of these other α-olefins to be used is at least 30 mo 1% or more in the copolymer. Polymerization can be carried out in the liquid phase or in the gas phase.

When polymerization is carried out in the liquid phase, for example, hexane.

Inert hydrocarbon solvents such as heptane, nonane, decane or kerosene may be used as the polymerization medium, but α
- The olefin itself can also be used as the reaction medium.

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 inert hydrocarbons mentioned in -I-. 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, and the polymerization pressure is atmospheric pressure -100 kg/am' (G), preferably 5-50 kg/crn' (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 adjust 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 and 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 1,000 ml 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 eliminates the need for a polymer purification process, making it extremely economical. Second, the stereoregularity of the polymer is extremely high. Isotactic index (hereinafter referred to as II)
This is indicated by the high value of It is extremely advantageous for producing polymers by gas phase polymerization without using solvents. Furthermore, (i) the particle shape of the resulting polymer is extremely good. That is, 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 IH5 extremely narrowly. There is very little amount of very small polymers, ie, fine powder. This enables stable production of polymers over a long period of time in liquid phase polymerization methods such as slurry polymerization and bulk polymerization, and gas phase polymerization methods.

In addition, it is easy to transport and recover the combined product, and the feeding to the granulator and processing and molding operations are facilitated, and productivity is greatly improved. It can suppress dust explosions caused by fine powder and is effective in preventing entrainment.

In addition, copolymerization causes less deterioration in the shape of the polymer particles and lower bulk specific gravity, making it easier to produce the copolymer.

Another major effect of the present invention is that even if the steps of drying the solid product (II) and prepolymerization are omitted, the same effects as in the prior invention can be obtained, and these steps can be omitted. Omission makes it possible to produce the solid product (II) very easily.

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

In the Examples and Comparative Examples, various properties that define the polymer
The method for determining -1 (or 7 (f1) is as follows.

(1) Melt flow rate 1 (abbreviated as MFR) is 8 ST
Based on M DI238(L).

(2) Polymer bulk ratio ii (abbreviated as BD) is AST
According to AD1895.

(3) The shapes of the solid product (■), solid product (11), and polymer particles were observed using an optical microscope.

In all Examples, the polymer (II) also had a nearly spherical shape.

(4) Polymer particle size distribution is JISZ 8801 Niyo 6
fiij according to JIS K 0069. Further, the particle size fraction 41 of the solid product (1) and the solid product (rr) was determined by Microtrac Analysis 1.1 manufactured by L'eeds & Nortbrup.

(5) Cumulative 50 of the particle size cumulative curve for the above particle size of 4J
The particle size of 111% by weight is the average particle size, and the uniformity index is the value obtained by dividing the particle size of 85% by weight by the particle size of 111% by weight.

(6) The amount of fine movement of a polymer is the ratio of the amount of polymer having a single particle size of less than 100 g m to the total amount.

(7) What is II(1)? In the case of liquid phase polymerization using an inert hydrocarbon II(1) = In the case of liquid phase polymerization and gas phase polymerization using α-olefin as a solvent (8) What is II(2)? In the case of liquid phase polymerization using inert hydrocarbon water J8 In the case of liquid phase polymerization and gas phase polymerization using α-olefin as a solvent Example 1 (+) Preparation power of supported solid catalyst component {Ifj tJ in a glass flask decan 50
5.7 g of magnesium jetoxide, 0.0 g of aluminum oxide. fi7g, n-butyl orthotitanate 17.
1 g, 19.8 g of 2-ethyl-1-hexanol, and 1.5 g of ethyl benzoate, without stirring. 13
It was heated to 0°C for 2 hours to dissolve. The homogeneous solution is
At 0°C, 51 g of silicon tetrachloride was added dropwise over 2 hours while stirring to precipitate a solid. After further stirring at the same temperature for 1 hour, 1.9 g of ethyl benzoate was added and reacted at 70°C for 1 hour. After this, the solid was washed with purified hexane to obtain a solid product (I). The solid product (I) total · °l
50 ml of sodium tetrachloride diluted with 50 ml of 1,2-dichloroethane! The mixture was reacted at 80°C for 2 hours with stirring, washed with purified hexane, and purified hexane was added without drying to obtain a hexane fg% solution.

50 g of solid product (II) was present during the suspension.

The operations described above and similar operations in subsequent Examples and Comparative Examples were all carried out under a nitrogen atmosphere.

The solid product (II) has a nearly spherical shape, and t]j
The average particle diameter was 21 μm, and the uniformity index was 1.44. 25℃,
The composition analysis result of the solid product (II) obtained by drying under reduced pressure (10-+mmHg) for 3 hours is Ti 3.24
Weight% (hereinafter referred to as %), benzoic 1'M ethyl 10.7
%, but(·xy group) 1.6% and 2-ethylhexanoxy group 2.2%.

(2) Production of polyolefin Stainless steel with nitrogen-substituted internal volume of 3 cm and multi-stage stirrer%
In a reactor, 1.5 mmol of triethylaluminum, 0.5 mmol of diethylaluminium chloride, 0.5 mmol of Pi-mylylmethyl + nmol I solid product (II)
4. in terms of T1 atoms. After addition of 10-' mg atoms of OX and 300 ml of hydrogen, the total pressure is 22 k at 70 °C.
Polymerization was carried out for 2 hours while continuously introducing propylene so as to give g/cm' (G). Thereafter, unreacted propylene was discharged to obtain 220 g of powdered polypropylene. The results are shown in the table. This powdered polypropylene had an average particle size of 620 gm and was difficult to grind.

Comparative Example 1 In Example 1, the solid product (II) was washed with purified hexane and then heated at 25°C under reduced pressure (10-n+mHg).
) A supported solid catalyst component was prepared in the same manner as in Example 1, except that the solid product (II) was dried for 3 hours, and the solid product (II) was used. Produced polypropylene.

Comparative Example 2 Solid product (T1) equivalent obtained in Comparative Example 1 3
Triethylaluminum IOmm cooled to O'C
Ethylene was suspended in 200mM of purified hexane containing 100 ml of olefin, and while stirring, added ethylene to the suspension at the same temperature so that the polymer yield was approximately log-polymer/g-solid product (!■). 511. 'I blew it for a while. Wash with purified hexane until triethylaluminum is no longer detected in the filtrate, and incubate at 25°C under reduced pressure at □o-1 m m tl.
g) After drying for 3 hours, the solid product (II[) was converted into (1
1.

Ti in the solid product (III) was 0.29%. Example 1 (2) except that the solid product ([) is used in place of the solid product (II) in Example 1 (2)
Polypropylene was produced in the same manner.

Example 2 (1) Preparation of supported solid catalyst component In a stainless steel flask, purified nonane 50 a
n, magnesium jetoxide 5.7g, ethylaluminum dichloride 0.1+52g, ethyl orthotitanate 17.2g, n-octatool 13.0g and p-
Mix 1.63 g of ethyl anisate and add 11 g of ethyl anisate while stirring.
It was heated to 0° C. for 3 hours to dissolve it. 50% of the homogeneous solution
℃, and while stirring, 58 g of ethyl silicon trichloride containing 1.98 g of p-ethyl anisate was added dropwise over 2.5 hours to precipitate a solid. After further stirring for 1 hour, the solid was washed with purified hexane to form a solid. Product (I) is 11I. The solid product (■) total 41 and toluene 3゜11! The mixture was mixed with 100 g of ethoxytitanium trichloride diluted with 100 g of ethoxytitanium trichloride, reacted at 110°C for 1 hour with stirring, washed with purified hebutane,
Without drying, butane was added to the purified mixture to form a heptane suspension. The solid product (n) is 10 in one suspension.
g.

The solid product (II) had a nearly spherical shape, an average particle size of 22#L layer, and a uniformity index of 1.44. 30℃, 3
The compositional analysis results of the solid product (II) obtained by drying under reduced pressure for hours showed that the Ti content was 3.05% and the ethyl anisate content was 8.8%.

(2) Production of polyolefin In a nitrogen-substituted autoclave with an internal volume of 3.6 tons, 6m5o1 of triethylaluminum was placed. Ethyl p-anisate 1. ．． 5 mmol and solid product (II) in terms of Ti atoms: 8. After adding OX 10-' 11 g atoms,
Introducing 500 layers of hydrogen together with 1 kg of liquid propylene,
Polymerization was carried out at 70°C for 1 hour. During that time, the total pressure is 32kg
/crn' (G). Thereafter, unreacted propylene was discharged to obtain 318 g of powdered polypropylene. The results are shown in the table. Powdered polypropylene has an average particle size of 490
It was ILm and was difficult to grind.

Comparative Example 3 The procedure of Example 2 was repeated except that the solid product (II) was washed with purified hebutane and then dried at 30°C under reduced pressure for 3 hours to obtain the solid product (II). A supported solid catalyst component was prepared in the same manner to produce polypropylene.

Comparative Example 4 3 g of the solid product (rr) equivalent obtained in Comparative Example 3 was suspended in 300 m of purified hexane containing 5 mmol of triethylaluminum cooled to 5°C in the presence of a small amount of propylene and stirred. At the same temperature, propylene was bubbled into the suspension for 3 hours so that the polymer yield was approximately 5 g of polymer/g of solid product (11). Washed with purified hexane and heated at 30°C under reduced pressure.
After drying for 3 hours, a solid product (III) was obtained. Ti in the solid product (III) was 0.48%. Example 2 (2) except that in (2) of Example 2, the solid product (m) is used instead of the solid product (II)
Polypropylene was produced in the same manner.

Example 3 (1) Preparation of supported solid catalyst component In a glass flask, 50 m of purified decane, 5.7 g of magnesium jetoxide, 0.424 g of diethylaluminium chloride, and 1 n-butyl orthotitanate were added.
7.1 g and 1-z thyl-1-hexanol 18.
6 g were mixed and heated to 130° C. for 1.5 hours with stirring to obtain a homogeneous solution. The homogeneous solution was heated to 70° C., 1.8 g of ethyl benzoate was added, and the mixture was stirred for 1 hour. 51 g of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred for 1 hour. Subsequently, ethyl benzoate 1
．． After adding 8 g and stirring for 1 hour, the solid was separated and washed with purified hexane to obtain a solid product (I). Using this solid product (I), a supported solid catalyst component was prepared in the same manner as in Example 1 (1).

The solid product (II) had a nearly spherical shape, an average particle size of 19 B'm, a uniformity index of 1.46, and a Ti content of 3.45% in the dry solid product (II).

(2) Production of polyolefin Purified hexane 12 was placed in a 2-liter autoclave purged with nitrogen, and 1.5 mmol of triethylaluminum was added.
and ethylaluminum sesquichloride 0.5 mmol
, p-ethyl anisate 0.5+wmol and solid product (II) 4.0% in terms of Ti atom. OX 10-'
After adding yxg atoms and 200 ml of hydrogen, the mixture was combined at 70° C. for 1 hour while continuously introducing propylene so that the total pressure was 10 kg/crrf (G). Thereafter, hexane-insoluble matter was filtered off and dried to obtain 75.2 g of powdered polypropylene. The results are shown in the table. This powdered polypropylene has an average particle size of 370p, rs
It was difficult to be crushed.

Comparative Example 5 In Example 3, after washing the solid product (II) with purified hexane, the solid product (m
) was obtained, and polypropylene was produced.

Examples 4 to 6 In Example 1, n-butyl orthotitanate 17.1
Using 23.9 g instead of g (Example 4),
Using 8.5 g of polyethyl titanate (pentamer) instead of n-butyl orthotitanate (Example 5), or using 18.9 g of carbolic acid instead of 2-ethyl-1-hexanol (Example 5) Example 1 except 6)
A supported solid catalyst component was prepared in the same manner as described above, and polypropylene was produced.

Example 7 In (2) of Example 3, di-l-
A propylene-butene copolymer was obtained in the same manner as in Example 3 (2) except that propylene containing phthene IOmo I% was used. Butene content in the copolymer is 3.8 mo
It was 1%.

Examples 8-9 In (+) of Example 2, first 0.88 g of ethyl acetate and then 0.97 g of ethyl acetate are used instead of ethyl P-anisate used in the two steps (Example 8) Alternatively, a supported solid catalyst component was prepared in the same manner as in Example 2 (1) except that 98 g of vanadium tetraJ11 was used instead of ethoxytitanium trichloride (Example 9), and the supported solid catalyst component was prepared in the same manner as in Example 3 (1). Polypropylene was produced in the same manner as in Example 3 (2) except that these supported solid catalyst components were used instead of 2).

Example IO In a stainless steel vibratory mill with an internal volume of 100 mm, 11.4 g of magnesium jetoxide and 1 aluminum chloride were added.
．． 1.34 g and 3.0 g of m-ethyl benzoin were added one after another, and 10 stainless steel poles (5 13 mm diameter and 5 10 mm diameter) were placed in a sealed container and co-pulverized at 30°C for 1 hour to form a finely powdered complex with a large specific surface area. The compound was obtained. Put 7.9 g of this complex compound into a glass flask, add 50 g of purified decane, and 17.1 g of n-butyl orthotitanate.
and 19.8 g of 2-ethyl-1-hexanol were added and heated to 130° C. for 2 hours with stirring to obtain a homogeneous solution. After making a homogeneous solution, a solid product (II) was prepared in the same manner as in Example 1 (1), and then in Example 1 (2).
Polypropylene was produced in the same manner.

Example 11 In the same manner as in Example 1 (1), solid product (I) was reacted with titanium tetrachloride in dichloroethane, and after washing with purified hexane, hexane and solid product (II) were in the same weight ratio. the solid product (II)
A polyolefin was produced in the same manner as in Example 1 (2) using the following.

The above results are shown in the table.

Table Price list 1. Fruit++1. ("I) g-polymer/mg original (-Ti・time (t2) spherical, nearly spherical, 〒li, granular (sai3) grain R1350JLII to JH710g++ percentage of polymer Togane (Togane 1%) or more Procedures Amendment: March 2, 1985 Manabu Shiga, Commissioner of the Patent Office) J.1) 1. Indication of the case 1. Patent Application No. 25,478 of 1982. 2. Title of the invention: Process for producing catalyst components for polyolefin production. 3. Relationship with the person making the amendment + 11 cases Patent applicant 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(207) Chisso Corporation Representative Sadao Nogi 4, Agent 4-4-15 Tsukiji, Chuo-ku, Tokyo (104) 6, No number of inventions increased by amendment 7, Specification subject to amendment Claims and Detailed Description of the Invention.

8. Contents of amendment Correct the statement as follows.

A.4'f51 The entire text of the claims is corrected as shown in the attached sheet.

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

(1) Page 11, lines 15-16 a) r 113+ 0
Ti(R')(C15) Sleeve 016 J rrt3(
OTi (011') (OR5) % 0Ill'J
D. Correct.

(2) "Contained in r" on page 20, line 14 is corrected to "used to obtain".

(3) In the third line from the bottom of the inversion, change ``in 1'' to ``used to obtain''.

(4) Change “0.1 to 2.0” in line 11 from the bottom of the same page to “0”
．． 1 to 3.0” and “0.5 to 2.5” to “0.5 to 2.5”.
Correct it to 0.

(5) On page 21, line 5, ``inside'' is corrected to ``used to obtain.''

(6) Insert "or" after "koxide" on page 22, line 5.

(7) Change “50-500” in the 6th line of the same page to “50-100”
Correction to O.J.

(8) On page 24, line 1, insert J chloride after “and”.

8. Attached Old Documents Attachments (Full text of claims) Above Attachments (Full text of claims) (1) C11) a, Magnesium alkoxide, aluminum halide, titanate ester, alcohol and as necessary A complex compound is obtained by heating and dissolving the organic acid ester (I) in an inert hydrocarbon solvent, or by co-pulverizing sour, magnesium alkoxide, aluminum halide and the organic acid ester (I), and the complex compound, The titanate ester and alcohol are heated and dissolved in an inert hydrocarbon solvent, (2) thus f1! The resulting solution is reacted with silicon halide and organic m ester (II) to precipitate a solid product (I), and the C3)liA solid product (I) is reacted with titanium halide and/or vanadium halide. , (4) The solid after the reaction is washed with a liquid inert hydrocarbon to obtain a 1-31 product (,n), and the solid product (II
) in the coexistence of at least 50% by weight of a liquid inert hydrocarbon.

(2) As aluminum halide, general formula A I
A compound represented by
n is a number from O to 3)
).

(3) General formula Ti(OR2)4 as titanate ester
orthotitanate ester represented by and/or polytitanate ester represented by general formula R3fOTi flat opening 0-R6, 12. B3. H4,15
and R6 is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and m is a number from 2 to 20). 1 Claim No. 1 (
1) The method described in D4.

(4) The method according to claim (1), wherein an aliphatic alcohol having 1 to 18 carbon atoms and/or an aromatic alcohol having 1126 to 24 carbon atoms is used as the alcohol.

(5) Claim No. (1) D1 uses an aliphatic carboxylic acid ester having 2 to 18 carbon atoms or an aromatic carboxylic ester having 8 to 24 carbon atoms as the organic S ester (I) or (II). Method described.

(e) For 1 mol of magnesium alkoxide, aluminum halide 0.01-Q, 5IIlol, orthotitanate ester and/or polytitanate ester (orthotitanate ester equivalent) 0.5-max mo
l, alcohol 0.5-e, omol and organic acid ester (I) 0.05-0.5 mol,
Inert hydrocarbon solvent core magnesium alkoxide 5
Claim (7) Dissolved by heating at 0 to +50°C for 5 minutes to 5 hours, per 1 mol of magnesium alkoxy,
Aluminum halide 0.01-0.5 mol. and organic acid ester (I) 0.05 to 0.5 mol
to form a complex compound, and orthotitanate ester and/or polytitanate ester (in terms of orthotitanate ester) 0.5-3,
0mol. Alcohol 0.5~e. Using omol,
Claim (1): Inert hydrocarbon solvent medium chain complex compound, orthotitanate ester and/or polytitanate ester, and alcohol are dissolved by heating at 50 to 150°C for 5 minutes to 5 hours. The method described in.

(8) General formula SiXnIi:-yl and or general formula SiXr+(OR8)4-n(
Here, X is C1 or Br, R' and R8 have 1 carbon number
-10 alkyl group, aryl group, or 3 or more carbon atoms
10 cycloalkyl group, n is a number from 1 to 4). 31. The method according to claim (1).

(9) Magnesium alkoxide lm is added to an inert hydrocarbon solution (hereinafter referred to as a homogeneous solution) of magnesium alkoxy 1 dissolved using aluminum halide, titanium ester, alcohol, and organic acid ester (I).
1 to 20 mo I of silicon halide and organic acid ester (II) o. +~Q. Bmol 50
The method according to claim (1), wherein the reaction is carried out at ~130° C. for 10 minutes to 5 hours.

(10) To precipitate solid product (I) from a homogeneous solution, react the solution with (!) organic acid ester (II) and then react with silicon halide (to precipitate 74 products, or (2) reacting the silicon halide simultaneously with the organic acid ester (II) to precipitate a solid, or (3) reacting the silicon halide to precipitate a solid and then reacting the organic acid ester (II). , or (4) the method according to claim (1), which uses a method combining any two or more of (1) to (■).

(ll) Titanium halide with the general formula TiXq (O
R9) to the compound represented by 4-q, or CI,
R9 is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and q is 1 to 4
The method according to claim (1), wherein the number of

(l2) After reacting solid product (I) with 3 to 50 mol of titanium halide and/or vanadium halide per 1 mol of magnesium alkoxide used for its production at 50 to 130°C for 10 minutes to 2 hours, The reactants were washed with an inert hydrocarbon solvent to form a solid product (
A method according to claim (1) for obtaining n>.

- Hand system first filj jJET? y+ Manabu Shiga, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 25,478 of 19812, Name of the invention, Process for producing catalyst components for producing polyolefins3, Relationship with the Nagisa case to be amended, Patent applicant Osaka 3-6-32 Nakanoshima, Kita-ku, Osaka, Japan (530)
(207,) Chisso Corporation Representative Sada Nogi H (.

4. Agent Tokyo Shinjuku 1〆, Shinjuku 2 ”I-[-18-1 (〒1
60) 5. Supplement 1F Order 1" Supplementary Supplement 6. No number of inventions increased by amendment 7. Column for detailed explanation of the invention in the specification to be amended.

8. Contents of amendment Correct the statement as follows.

Change “0.5 to 1.5” in the second line from the bottom of page 20 to “0.5”
~． Corrected to 2.0.

that's all

Claims (1)

[Scope of Claims] (1) ■a, magnesium alkoxide, aluminum halide, titanate ester, alcohol, and optionally organic acid ester (I) are dissolved by heating in an inert hydrocarbon solvent, or Magnesium alkoxide, aluminum halide and organic acid ester (I
) to form a complex compound, and the complex compound, titanate ester, and alcohol are heated and dissolved in an inert hydrocarbon solvent, and the silicon halide and organic acid ester ( II) to precipitate a solid product (I), () react titanium halide and/or vanadium halide to the solid product (I), and (4) convert the solid after the reaction into a liquid. A solid product (II) is obtained by washing with an inert hydrocarbon of at least 50% by weight of the solid product (II) in the presence of at least 50% by weight of a liquid inert hydrocarbon. A method for producing a catalyst component for polyolefin production. (2) As aluminum halide, general formula AIX+
+rl-n compound (as shown,
is a number from O to 3).
The method described in section. (3) General formula Ti(OR2)4 as titanate ester
- to the orthotitanate ester represented by and or the polytitanate ester represented by the general formula R3+ 0Ti(R')(R5) tO-R' te, 12. R3
, R4, R'l and R6 are an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and m is a number from 2 to 20). The method described in section (1). (4) The method according to claim (1), in which an aliphatic alcohol having 1 to 18 carbon atoms and/or an aromatic alcohol having 6 to 24 carbon atoms is used as the alcohol. (5) Claim (1) in which an aliphatic carboxylic acid ester having 2 to 18 carbon atoms or an aromatic carboxylic ester having 8 to 24 carbon atoms is used as the organic acid ester (I) or (II). the method of. (6) For 1 mo I of magnesium alkoxide,
Aluminum halide 0.01-0.5 mol, ortho titanium butyester and/or polytitanate ester (ortho titanate ester equivalent) 0.5-8, O
mol and organic S ester (I) 0.05-0
．． 5 mol of the inert hydrocarbon solvent core magnesium alkoxide is heated at 50 to 150° C. for 5 minutes to 5 hours to dissolve the method according to claim (1) d. (7) For 1 mol of magnesium alkoxide,
0.01-0.5 mol of aluminum halide and 0.05-0.5 a+ol of organic acid-ester (I)
A complex compound is obtained by co-pulverizing the complex compound using an orthotitanate ester and/or a polytitanate ester (in terms of an orthotitanate ester) of 0.5 to 3. O
mol, alcohol 0.5-B, Omol, inert hydrocarbon solvent medium chain complex compound, orthotitanate ester and/or polytitanate ester, and alcohol are heated at 50-150°C for 5 minutes to 5 hours to dissolve. The method according to claim (1). (8) General formula SiX*rlni n and or general formula SiX* (OR' )4-n as silicon halide
(Here, x is C1 or Br, n' and B@ are alkyl groups having 1 to 10 carbon atoms, aryl groups, or 3 carbon atoms
The method according to claim 1, wherein n is a number from 1 to 4). (9) Add magnesium alkoxide to an inert hydrocarbon solvent solution (hereinafter referred to as homogeneous solution) prepared by dissolving aluminum halide, titanate, alcohol, and organic acid ester (I).
For ll01, silicon halide 1~2G+eo
l and organic acid ester (II) 0.1-0.8 mo
1. The method according to claim 1, wherein 1 is reacted at 50 to 130° C. for 10 minutes to 5 hours. (1O) In precipitating the solid product (I) from a homogeneous solution, the solution is reacted with (1) an organic acid ester (II) and then reacted with silicon halide to precipitate a solid; A silicon halide is reacted simultaneously with the organic acid ester (II) to precipitate a solid, or (ii) a silicon halide is reacted to precipitate a solid, and then an organic acid ester (II') is reacted; The method according to claim (1), which uses a method combining any two or more of +i &
) 4-(In the compound represented by 1, X is CI, R
9 is an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 10 carbon atoms, and q is a number of 1 to 4). . (12) Solid product (I) contains 3 to 50 wo per mol of magnesium alkoxide used in its production.
After reacting the titanium halide and/or vanadium halide of I at 50 to 130 °C for 10 minutes to 2 hours, the reaction product is washed with an inert hydrocarbon solvent to obtain a solid product (II). A method according to claim (1). (13) The method according to claim (1), in which an aromatic carboxylic acid ester having 8 to 24 carbon atoms is used as the organic acid ester. (14) The method according to claim (1), in which the α-olefin is polymerized in a gas phase.