JPH0745540B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a solid catalyst component for olefin polymerization. More specifically, the catalyst component containing a magnesium compound as a main supporting material and titanium halide as a supported component, which is a solid catalyst component for olefin polymerization having improved storage stability, thermal stability and abrasion resistance. Manufacturing method.

[Technology of prior application and its problems]

Previously, the inventors of the present invention, in Japanese Patent Application No. 59-208775, a novel method for producing a solid catalyst component (hereinafter referred to as the following) having high polymerization activity, high stereoregularity, and giving an olefin polymer having a good particle shape. The desired catalyst production method) was proposed.

However, the solid catalyst component obtained in the prior application is stable for a long period of time when stored at 30 ° C. or lower, but the catalyst performance is apt to change when stored at 40 ° C. or higher, and the solid catalyst component is produced on a large scale. Occasionally, there was a problem that the powder was easily ground in the production apparatus, and a fine powder solid catalyst component was generated.

The storage temperature of 30 ° C. or lower means that the container of the solid catalyst component needs to be kept in a semi-cold state, and the storage, transportation or packaging cost of the industrial catalyst agent requires semi-cooling. The cost is higher than that of the case where it is not, and it is difficult to maintain a sufficiently long shelf life even if it is kept in a semi-cooled state. Further, if fine powder is generated during the production of the solid catalyst, it is difficult or economical to separate and remove the fine powder, and if an olefin polymerization catalyst is constituted by using the component containing the fine powder and used for olefin polymerization. The increased production of fines of olefin polymer results in adverse consequences with regard to post-production handling and quality uniformity of the polymer. It is a well-known fact to those skilled in the art that the form of the Ziegler-Natta solid catalyst component and the form of the olefin polymer obtained by using the component are in a similar relationship.

[Object of the Invention]

The present inventors have been researching the above-mentioned problems, but in the catalyst production method of the prior application, the solid product (I) precipitated from the solution state was used in the presence of an organoaluminum compound in a small amount of carbon number. When the polymerization treatment is carried out with two or more α-olefins, the final solid product obtained, even if the storage temperature thereof is maintained at a temperature significantly exceeding normal temperature (hereinafter referred to as ultra-normal temperature) such as 40 ° C., Its catalytic activity is not substantially reduced, and during the production of the solid catalyst component or during the subsequent handling or use (Note: preactivation or polymerization)
In the above, the present invention was found by finding the fact that the above-mentioned fine powder is hardly generated. Incidentally, the prepolymerization treatment is
From the point of view of the solid product (I), the so-called pre-activation of α-olefin treatment of the combination of the final solid carrying the titanium compound and the organoaluminum compound (catalyst) is the technical The meaning is different. The solid product (I) possesses polymerization activity because the product contains a polytitanate ester having a specific chemical structure.

As is clear from the above description, the object of the present invention is to solve the above-mentioned problems, improve storage stability, thermal stability and abrasion resistance, have high polymerization activity, high stereoregularity and particles. An object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, which gives an olefin polymer having a good shape.

[Constitution / Effect of Invention]

 The present invention has the following configurations.

(1) In a method for producing a solid catalyst component for olefin polymerization in which titanium halide, vanadyl halide or vanadium halide is supported on a carrier whose major component is an Mg compound precipitated from a solution state, I. Halide, orthotitanate represented by the general formula Ti (OR ¹ ) ₄ and / or polytitanate represented by the general formula R ² O—Ti (OR ³ ) (CR ₄ ) _m O—R ⁵ (here R ¹ , R ² , R ³ , R ⁴ and R ⁵
Is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is a number of 2 to 20), and a saturated or unsaturated monovalent group having 1 to 20 carbon atoms. Alternatively, a polyhydric alcohol is mixed and dissolved in an inert hydrocarbon solvent to obtain (Component A), and II. The (Component A) contains an aliphatic or aromatic mono- or polycarboxylic acid having 2 to 24 carbon atoms. Acid ester (hereinafter referred to as organic acid ester), a general formula AlX _n ▲ R ⁸ ₃ ▼ _-n (where X is Cl or Br, and R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 carbon atoms).
An aluminum halide represented by 20 cycloalkyl groups, n is a number from 0 to 3, and a general formula SiX _l ▲
R ⁶ ₄ ▼ _-l or SiX _p (OR ⁷ ) _4-p (where X is Cl or
Br, R ⁶ and R ⁷ are each an alkyl group having 1 to 20 carbon atoms,
An aryl group or a cycloalkyl group having 3 to 20 carbon atoms, l
Or p is a number from 1 to 4) (component B) composed of a silicon halide represented by the formula (3) is reacted to precipitate a solid (hereinafter referred to as a solid product (I)), and III. I) is preliminarily polymerized with an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound to obtain a solid product (II). IV. The solid product (II) has the general formula TiX _q (OR ⁹ ) _4-q (wherein X is Cl or Br, R ³ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4) Is a titanium halide and / or a general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t (where X is Cl or Br, R ¹⁰ and R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, s1 to 3
In which t is a number from 1 to 4) (component C) consisting of vanadyl halide or vanadium halide is reacted to form a solid (hereinafter referred to as a solid product (III)). A method for producing a solid catalyst component for polymerization.

(2) The method according to (1) above, wherein 0.01 g to 500 g of α-olefin is reacted with 1 g of titanium atom in the solid product (I), (II) or (III).

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

First, the stage I will be described.

(Component A) is obtained by reacting and dissolving components and in an inert hydrocarbon. The ingredients are
It is anhydrous magnesium dihalide. As anhydrous magnesium halide, anhydrous magnesium chloride and anhydrous magnesium bromide can be used. Anhydrous is these "anhydrous"
It may contain a trace amount of water as much as a commercially available product commercially available as a compound.

The component is a titanate ester. The titanic acid ester is an orthotitanic acid ester represented by Ti (OR ¹ ) ₄ and a polytitanic acid ester represented by R ² O—Ti (OR ³ ) (OR ⁴ ) _m O—R ⁵ . Where R ¹ , R ² ,
R ³ , R ⁴ and R ⁵ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is a number of 2 to 20. Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, i-propyl orthotitanate, orthotitanate n-
Butyl, orthotitanate i-butyl, orthotitanate n
-Amyl, 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, orthotitanate esters, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, polytitanate i -Propyl,
Polytitanate esters such as n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate and cyclohexyl polytitanate can be used.

The ingredient is alcohol. Aliphatic saturated and unsaturated alcohols can be used as alcohols.
Specifically, methyl alcohol, ethyl alcohol, n
-Propyl alcohol, i-propyl alcohol, n-
In addition to monohydric alcohols such as butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol and allyl alcohol, polyalcohols such as ethylene glycol, trimethylene glycol and glycerin are also available. Polyhydric alcohols can also be used. Of these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferable.

Inert hydrocarbon solvents used to dissolve the components, and include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, tetrachloride. Mention may be made of halogenated hydrocarbons such as carbon, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and 0-dichlorobenzene. Of these, aliphatic hydrocarbons are preferable.

The following methods may be mentioned as specific methods for reacting and dissolving the components and in an inert hydrocarbon solvent. That is, the components and are mixed in an inert hydrocarbon solvent in any order, and the suspension is heated with stirring. The components and are heated in an inert hydrocarbon solvent with stirring to add the components to the solution. Adding, heating the ingredients and in an inert hydrocarbon solvent with stirring, then adding the ingredients, or heating the ingredients and in an inert hydrocarbon solvent with stirring, then adding the ingredients, and so on.

Although any of the above methods can be adopted, the method is preferable because it is extremely easy to operate.

Heating is required to dissolve the components and in an inert hydrocarbon solvent. The heating temperature is 40 ~
The temperature is 200 ° C, preferably 50 to 150 ° C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours. The amount of the component used is 0.1 to 2 mol, preferably 0.5 to 1.5 mol when the former is orthotitanate, relative to 1 mol of the component, and similarly, in the case of polytitanate, the orthotitanate is converted to orthotitanate. An equivalent amount of acid ester may be used. The amount of the component used is 0.1 to 5 mol, preferably 0.5 to 4 mol, per 1 mol of the component.

It is easier to dissolve the component and the amount of the component to be used as much as possible with respect to the component. However, when such component (component A) is dissolved, an extremely large amount of silicon halide must be used. In addition to solidification, solidification itself becomes difficult, and even if solidification is achieved, controlling the particle shape becomes extremely difficult. Further, when the component and the amount of the component used are too small, the component does not dissolve in an inert hydrocarbon solvent, the supported solid catalyst component is in an amorphous form, and a supported solid catalyst component having the intended performance of the present application is produced. I can't. The amount of the inert hydrocarbon solvent used is 0.1 to 5, preferably 0.3 to 3, with respect to 1 mol of the component.

Next, Stage II will be described.

(Component B) consists of the components, and. The component is an organic acid ester. As organic acid ester,
Methyl acetate, ethyl acetate, n-propyl acetate, i-acetic acid
Propyl, n-butyl acetate, ethyl propionate, n-propyl propionate, i-butyl propionate, ethyl butyrate and phenyl acetate, and other aliphatic carboxylic acid esters, methyl benzoate, ethyl benzoate, methyl toluate, toluic acid Aromatic carboxylic acid esters such as ethyl, methyl anisate, ethyl anisate, phenyl anisate, diethyl phthalate, di-n-butyl phthalate and di-i-butyl phthalate can be used.

Component is aluminum halide represented by the general formula AlX _n R ⁸ _3-n. Here, X is Cl or Br, R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or 3 to 20 carbon atoms.
Is a cycloalkyl group, and n is a number from 0 to 3. Specifically, aluminum trichloride, ethyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum chloride, dipropyl aluminum chloride, triethyl aluminum, tributyl aluminum, triphenyl aluminum, diphenyl aluminum chloride, tricyclohexyl aluminum, dicyclohexyl. Aluminum chloride, aluminum tribromide, ethyl aluminum dibromide and the like can be mentioned.

The component is represented by the general formula SiX _l ▲ R ⁶ ₄ ▼ _-l or SiX _p (OR ⁷ ) _4-p
Is a halogenated silicon. Where X is Cl
Alternatively, Br, R ⁶ and R ⁷ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 2 carbon atoms, and 1 or p is a number of 1 to 4. Specifically, SiX _l
▲ R ⁶ ₄ ▼ _{-l represents} silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, ethyl silicon tribromide, Diethyl silicon chloride,
Such as dibutyl silicon dichloride and triethyl silicon chloride, as SiX _p (OR ⁷ ) _4-p , silicon tetrachloride, silicon tetrabromide, methoxysilicon trichloride, ethoxysilicon trichloride, propoxysilicon trichloride, butoxysilicon trichloride, Phenoxy silicon trichloride, ethoxy silicon tribromide, dimethoxy silicon dichloride, diethoxy silicon dichloride, dibutoxy silicon dichloride, diphenoxy silicon dichloride, dimethoxy silicon dibromide, trimethoxy silicon chloride and triethoxy silicon chloride Can be mentioned. It is also possible to use mixtures of the compounds mentioned. Among them, silicon tetrachloride is preferable. These components may be diluted with the above-mentioned inert hydrocarbon solvent before use.

Next, the reaction between (Component A) and (Component B) will be described.
The solid product (I) is obtained by the reaction of (component A) and (component B). This reaction is Add (Component B) to (Component A), b. Add (Component A) to (Component B),
Or c. By adding a part of the component (component B) to the (component A) and then adding the remaining component of the (component B) or adding it to the remaining component of the (component B). You can

Specifically, for example, there are the following methods. That is, after the component A is reacted with the component and / or simultaneously with the component, the components are reacted to precipitate the solid product (I). The components and and are reacted simultaneously to precipitate a solid product (I). After the components are reacted to deposit a solid, the components are subsequently and / or simultaneously reacted to give a solid product (I). After reacting a mixture with a component and / or a reaction product, the components are reacted to precipitate a solid product (I). After the components are reacted to precipitate a solid, a mixture with the components and / or a reaction product is reacted to obtain a solid product (I). Alternatively, there can be mentioned a method in which any two or more of are combined. Either method can be adopted. A solid does not precipitate even if a component and / or a component is mixed or reacted with (component A). (Component A) or (Component A) and the component and / or the mixture or reaction product of the components is a homogeneous solution. Ingredients are required to precipitate solids from these homogeneous solutions. As the addition method according to the above-mentioned (1) to (3), it is usually preferable to add the component and the component to the (component A), but the component can be added to the (component A) or the (component A) is added to the component. You can also Since the particle shape of the solid product (II) is controlled by the particle shape of the solid product (I), the particle shape can be controlled by controlling the component and the (component A) or the (component A) and the component and / or the mixture of the components. Alternatively, the reaction with the reactant is extremely important.

The usage ratio of (Component A) to the components and is as follows. That is, the amount of the component used is 0.05 to 0.7 mol, relative to 1 mol of the component constituting (Component A) as a raw material,
Preferably 0.1-0.6 mol, the amount of the component used is 0.005-0.5
The molar amount, preferably 0.01 to 0.4 mol, and the amount of the component used is 0.1 to 50 mol, preferably 1 to 20 mol. These components may be used at one time or may be used in several stages. The reaction temperature of (Component A) and (Component B) is −
The temperature is 40 to + 180 ° C., preferably −20 to + 150 ° C., and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 3 hours per step. The solid product (I) precipitated by the reaction of (component A) and (component B) may be subjected to the subsequent reaction in the next step, but it should be washed with the inert hydrocarbon solvent described above. Is preferred. This is because unreacted substances or by-products present in the solution may interfere with the subsequent reaction. Thus, a solid product (I) having a spherical shape or a shape close to a spherical shape is obtained.

Next, step III will be described.

In this step, the solid product (I) obtained in the previous step II is brought into contact with a small amount of an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound and prepolymerized to give a solid product (II). The significance of the prepolymerization treatment is as described above. At that time, the inert hydrocarbon solvent may or may not be present. As the organoaluminum compound, a compound represented by AlX _r ∑R ¹² ₃ ▼ _-r described later can be used. Α- with 2 or more carbon atoms
As the olefin, ethylene, propylene, butene-
1, pentene-1, hexene-1, octene-1, 4-
Besides methylpentene-1 and 3-methylpentene-1, butadiene, isoprene, 1,4-pentadiene, methyl-1,4-hexadiene and the like can be mentioned. Inert hydrocarbon solvents can include hexane, heptane, nonane, decane and kerosene. As a method for bringing the solid product (I) into contact with the α-olefin to preliminarily polymerize it, for example, the solid product (I) is mixed with the organoaluminum compound in an inert hydrocarbon solvent, and then the α-olefin is supplied. The solid product (I) is suspended in an inert hydrocarbon solvent in which an organoaluminum compound is dissolved, and then α-olefin is supplied. In addition, the solid product (I) may be added to an inert hydrocarbon solvent in which an organoaluminum compound and an α-olefin are dissolved, and an α-olefin may be further supplied if necessary. The α-olefin is fed so that the amount of the polyolefin to be prepolymerized is 0.001 to 1000 g, preferably 0.01 to 500 g, per 1 g of the solid product (I). The amount of the organoaluminum compound used is the amount of titanium atom 1 contained in the solid product (I).
The amount is 0.1 to 500 mol, preferably 0.5 to 100 mol, based on mol. The amount of the inert hydrocarbon solvent used is 0 to 1000 ml, preferably 5 to 500 ml per 1 g of the solid product (I).

The temperature during prepolymerization is -20 to + 50 ° C, preferably 0 to
The temperature is 30 ° C. and the time is 1 minute to 5 hours, preferably 3 minutes to 3 hours. In the prepolymerization stage, it is also possible to coexist a carboxylic acid ester such as ethyl benzoate, methyl toluate and ethyl anisate, or a silane compound such as phenyltriethoxysilane, diphenyldimethoxysilane and methyltriethoxysilane. The amount used is 0 to 2 per 1 mol of the organoaluminum compound.
The amount is preferably 0 to 0.5 mol. The solid product (I) is covered with polyolefin. Wash with the previously mentioned inert hydrocarbon solvent until no organoaluminum compound is detected in the filtrate. A solid product (II) is thus obtained.

Next, step IV will be described.

Ingredient (C) consists of ingredients and / or ingredients. The component is a titanium halide represented by the general formula TiX _q (OR ⁹ ) _4-q . Here, X is Cl or Br, and R ⁹ has 1 to 1 carbon atoms.
20 is an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4. Specifically, titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride,
Butoxy titanium trichloride, hexoxy titanium trichloride, octoxy titanium trichloride, phenoxy titanium trichloride, cyclohexoxy titanium trichloride, ethoxy titanium tribromide, butoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dichloride Dipropoxytitanium chloride, dibutoxytitanium dichloride, dioctoxytitanium dichloride, diphenoxytitanium dichloride, dicyclohexoxytitanium dichloride,
Examples include diethoxy titanium dibromide, dibutoxy titanium dibromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, triethoxy titanium bromide and triphenoxy titanium bromide. it can. Titanium halides other than titanium tetrachloride or titanium tetrabromide can be produced by the reaction of titanium tetrahalide with orthotitanate, but in the reaction of step III, tetrahalogenate is used instead of the one produced by the above reaction. Mixtures of titanium oxide and orthotitanate can also be used. As the orthotitanate, the same orthotitanate as described above can be used. Among these titanium halides, titanium tetrachloride is most preferable.

The component has the general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ).
It is vanadyl halide or vanadium halide represented by _4-t . Here, X is Cl or Br, R ¹⁰ and R ¹¹ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and s is 1 to
3 and t are numbers 1 to 4. Specifically, vanadyl trichloride, vanadyl tribromide, methoxy vanadyl dichloride, ethoxy vanadyl dichloride, butoxy vanadyl dichloride, phenoxy vanadyl dichloride, cyclohexoxy vanadyl dichloride,
Ethoxyvanadyl dibromide, dimethoxyvanadyl chloride, diethoxyvanadyl chloride, diphenoxyvanadyl chloride, diethoxyvanadyl bromide, vanadium tetrachloride, vanadium tetrabromide, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, Phenoxy vanadium trichloride, cyclohexoxy vanadium trichloride, ethoxy vanadium tribromide, dimethoxy vanadium dichloride, diethoxy vanadium dichloride, dibutoxy vanadium dichloride, diphenoxy vanadium dichloride, diethoxy vanadium dibromide, triethoxy chloride Vanadium, triphenoxy vanadium chloride, triethoxy vanadium bromide and the like can be mentioned. Among these vanadyl halides or vanadium halides, vanadyl trichloride and vanadium tetrachloride are preferable.

The components and the components can also be used in the reaction with the solid product (II) as mixtures and / or reactants thereof. It can also be used after diluting it with the above-mentioned inert hydrocarbon solvent.

Next, the reaction between the solid product (II) and (component C) will be described. In the reaction of the third stage, (Component C) is added to the solid product (II) suspended in the above-mentioned inert hydrocarbon solvent, or the solid product (II) or its suspension is added to (Component C). It can be carried out by a method such as adding a turbid solution.

The amount of the component or used is 1 to 100 moles, preferably 3 to 50 moles, relative to 1 mole of anhydrous magnesium dihalide which is a constituent raw material of the solid product (II).

The reaction temperature of the solid product (II) and (component C) is 40 to 200.
℃, preferably 50 ~ 150 ℃, reaction time 5 minutes ~ 5 hours,
It is preferably 10 minutes to 3 hours. After the reaction, solids are separated by filtration or decantation and then washed with an inert hydrocarbon solvent to remove unreacted substances and by-products.
A solid product (III) is thus obtained. The solvent used for washing is a liquid inert hydrocarbon. Specific examples thereof include aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane and kerosene.

The solid product (III) thus obtained can be dried and stored as a powder, or can be suspended and stored in the above-mentioned inert hydrocarbon solvent.

It is also possible to further pre-polymerize the solid product (III) before producing the olefin polymer using the solid product (III). In step III, prepolymerization can be carried out in the same manner as in step III except that the solid product (III) is used instead of the solid product (I). This prepolymerization treatment is distinguished from so-called preactivation in that the solid product after the treatment is not used for the regular polymerization of the olefin.

Next, a method for producing an α-olefin polymer will be described. The solid product (III) can be used as a catalyst for producing an α-olefin polymer by combining it with an organic aluminum compound and preferably an organic acid ester as a solid catalyst component. As the organoaluminum compound to be combined, a compound represented by AlX _r ∑R ¹² ₃ ▼ _-r can be used. Here, X is Cl, R ¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and r is a number of 0 to 2. Specifically, triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl aluminum, tricyclopentyl aluminum, tricyclohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum chloride, ethyl aluminum sesquichloride. And ethylaluminum dichloride and the like. Among them, triethylaluminum alone or a mixture of two kinds of organic aluminum compounds such as triethylaluminum and tri-i-butylaluminum, triethylaluminum and diethylaluminum chloride and triethylaluminum and ethylaluminum sesquichloride, or triethylaluminum and tri-i-butyl. It is preferable to use a mixture of aluminum and three kinds of organic aluminum compounds such as ethylaluminum sesquichloride.

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

The solid product (III), the organoaluminum compound and the organic acid ester may be combined by a method such as the solid product (II
I), an organoaluminum compound and an organic acid ester are independently fed to a polymerization vessel, a mixture of an organoaluminum compound and an organic acid ester and a solid product (III) are independently fed to a polymerization vessel, a solid product (III) , A mixture of an organic aluminum compound and an organic acid ester is supplied to a polymerization vessel, and any method can be adopted. However, in some cases or is preferred. When the three components are combined as described above, each component or any component may be dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane and kerosene before use. . The temperature in the case of mixing before feeding to the polymerization vessel as described above is -50 to + 50 ° C, preferably -30 to +30.
C. and time are 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is 10 to 1000 mol, preferably 50 to 500 mol, per 1 mol of titanium atom contained in the solid product (II) as the solid catalyst component. The amount of the organic acid ester used is 0.01 to 1 mol, preferably 0.05 to 0.7 mol, per 1 mol of the organic aluminum compound. When the mixed organoaluminum compound or mixed organic acid ester is used, the total number of moles thereof may fall within the above range.

The solid product (II as the solid catalyst component according to the present invention
The catalyst obtained by the combination of I), an organoaluminum compound and preferably an organic acid ester is used to produce an α-olefin polymer 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 and 3-methylpentene-1 are used. can do. In the polymerization of these α-olefins,
It includes not only homopolymerization but also copolymerization with one or two or more other α-olefins having 2 or more carbon atoms. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-pentadiene and methyl-1,4 in addition to the α-olefin having 3 or more carbon atoms described above.
Mention may be made of hexadiene and the like. The amount of the other α-olefins used is such an amount that 50 mol% or less is contained in the copolymer obtained by the copolymerization.
The polymerization can be carried out in the liquid phase or the gas phase. When the polymerization is carried out in the liquid phase, for example, hexane, heptane,
An inert hydrocarbon solvent such as nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may be used as the reaction medium. When carrying out the polymerization in the gas phase, in principle no reaction medium is used, but it is also possible to use either the catalyst or any of its components dissolved or suspended in the abovementioned inert hydrocarbons. The polymerization is carried out by bringing the catalyst into contact with the α-olefin in the polymerization vessel. Polymerization temperature is 40 ~ 200 ℃, preferably 5
The polymerization pressure is 0 to 150 ° C., and the polymerization pressure is atmospheric pressure to 100 kg / cm ² G, preferably 5 to 50 kg / cm ² G. The polymerization can be carried out by any of a batch type, a semi-continuous type and a continuous type, but industrially a continuous type polymerization is preferred. It is also possible to carry out the polymerization by multistage polymerization under 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 production or storage of the solid catalyst component described above, the preparation of the catalyst and the production of the polymer must be carried out in an atmosphere of an inert gas such as nitrogen or helium, but in some cases, even in an atmosphere of a monomer or under vacuum conditions. It can be carried out.

The effects obtained by the present invention are as follows.

The solid catalyst component for olefin polymerization according to the present invention has excellent storage stability and thermal stability. It is extremely important industrially to be able to store it stably for a long period of time regardless of the outside temperature. The storage can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Further, the solid catalyst component for olefin polymerization according to the present invention is excellent in abrasion resistance. The component is not susceptible to grinding during use, that is, not only in the olefin polymer production process but also in the catalyst production process. This prevents the formation of finely divided catalyst,
As a result, it means preventing the formation of finely divided olefin polymer. As a result, it was possible to solve the entrain problem that tends to occur during the production of olefin polymers in the gas phase polymerization process.

Another effect of the present invention is that the polymerization activity is extremely high and removal of the residual catalyst in the olefin polymer is not necessary. In addition, it is possible to produce an olefin polymer having a high stereoregularity and a good particle shape.

The present invention will be described below with reference to examples.

Example 1 (1) Preparation of solid catalyst component In a glass flask, 30 ml of decane, 4.8 g of anhydrous magnesium chloride, 17 g of n-butyl orthotitanate and 2 were added.
-Ethyl-1-hexanol (19.5 g) was mixed and heated at 130 ° C for 1 hour with stirring to be dissolved to obtain a uniform solution. The solution was brought to room temperature, and 3.7 g of ethyl p-toluate was added, followed by 0.42 g of diethylaluminum chloride, and then 70
Heat to ℃ for 1 hour and continue stirring with silicon tetrachloride
52 g was added dropwise over 2.5 hours to precipitate a solid, which was further heated to 70 ° C. for 1 hour. The solid was separated from dissolution and washed with hexane to give a solid product (I).

The Ti content of the solid product (I) was 3.3% by weight (hereinafter referred to as%). The total amount of the solid product (I) was suspended in 500 ml of hexane containing mmol of triethylaluminum cooled to 10 ° C., and the polymer yield was 1.0-polymer / g-solid in suspension at the same temperature while stirring. Ethylene was introduced for 1 hour to give the product (I). The solid product (II) was obtained by washing with hexane until no triethylaluminum was detected in the filtrate.

The whole amount of the solid product (II) was mixed with 50 ml of titanium tetrachloride dissolved in 50 ml of 1,2-dichloroethane and stirred at 80 ° C.
The mixture was reacted for 2 hours, washed with hexane and dried to give a solid product (III). The solid product (III) had a particle shape close to a sphere and contained 0.97% Ti and 61.0% polyethylene.

(2) Production of α-olefin polymer In a stainless reactor equipped with a multi-stage stirrer and having an internal volume of 3 substituted with nitrogen, 1.5 mmol of triethylaluminum, 0.5 mmol of ethylaluminum sesquichloride, 0.5 mmol of ethyl p-anisate, and a solid product ( After adding 0.01 mg of Ti atom and 1.0 of hydrogen, the polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 22 kg / cm ² G. Then, unreacted propylene was discharged to obtain 213 g of powdery polypropylene.
The particle shape of the polypropylene was close to spherical, MFR3.0, bulk density 0.45, no odor was observed, and boiling heptane extraction residual ratio (6 hours) was 97.0%.

(3) Attrition resistance test In a nitrogen atmosphere, using a magnet drive type circulation pump (magnet pump MD-10 type manufactured by Iwaki),
A solution prepared by suspending 30 g of the solid product (III) in hexane 1 was circulated for 4 hours under the conditions of a flow rate of 1.1 / min and a temperature of 25 ° C., and then the olefin was treated in the same manner as in Example 1 (2). A polymer was produced.

Examples 2 to 3 The solid product (III) obtained in Example 1 was used in a nitrogen atmosphere 4
The mixture was stored at 0 ° C., and after 3 months (Example 2) and 6 months (Example 3), an olefin polymer was produced in the same manner as in Example 1 (2).

Example 4 In obtaining the solid product (II) from the solid product (I) in (1) of Example 1, the polymer yield was adjusted to 10 g-polymer / g-solid product (I). Preparation of a solid catalyst component, production of an olefin polymer ((1) of Example 4) and abrasion resistance test ((2) of Example 4) were conducted in the same manner except that ethylene was introduced at 15 ° C. for 3 hours. I did.

Comparative Example 1 Same as Example 1 except that the whole amount of the solid product (I) obtained in the same manner as in (1) of Example 1 was converted to the solid product (II) equivalent without prepolymerization. Preparation of a solid catalyst component, production of an olefin polymer ((1) of Comparative Example 1) and an abrasion resistance test ((2) of Comparative Example 1) were performed.

Comparative Examples 2 to 3 The solid product (III) equivalent obtained in Comparative Example 1 was stored at 40 ° C. under a nitrogen atmosphere, and after 3 months (Comparative Example 2) and 6 months (Comparative Example 3), Examples An olefin polymer was produced in the same manner as in (2) of 1.

Example 5 Solid product (I) 10 obtained in the same manner as in (1) of Example 1.
g was cooled to 15 ° C., suspended in hexane 1 containing 52 mmol of triethylaluminum and 10 mmol of methyl toluate, and the polymer yield in the suspension was 5.0 g-polymer / g-solid at the same temperature while stirring. Propylene was introduced for 3 hours so that the product (I) was obtained. After washing with hexane to obtain a solid product (II), a solid catalyst component was prepared and an olefin polymer was produced in the same manner as in Example 1 ((1) in Example 5).
And a body grindability test ((2) of Example 5) was performed.

[Brief description of drawings]

The figure is a flow sheet showing the steps involved in carrying out the method of the present invention.

Claims (2)

[Claims] 1. A method for producing a solid catalyst component for olefin polymerization, comprising titanium halide, vanadyl halide or vanadium halide supported on a carrier comprising a Mg compound precipitated from a solution state as a main constituent. Magnesium dihalide, orthotitanate represented by the general formula Ti (OR ¹ ) ₄ and / or polytitanate represented by the general formula R ² O—Ti (OR ³ ) (CR ⁴ ) _m O—R ⁵ R ¹ , R ² , R ³ , R ⁴ and R ⁵
Is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is a number of 2 to 20), and a saturated or unsaturated monovalent group having 1 to 20 carbon atoms. Alternatively, a polyhydric alcohol is mixed and dissolved in an inert hydrocarbon solvent to obtain (Component A), and II. The (Component A) contains an aliphatic or aromatic mono- or polycarboxylic acid having 2 to 24 carbon atoms. Acid ester (hereinafter referred to as organic acid ester), a general formula AlX _n ▲ R ⁸ ₃ ▼ _-n (where X is Cl or Br, and R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 carbon atoms).
An aluminum halide represented by 20 cycloalkyl groups, n is a number from 0 to 3, and a general formula SiX _l ▲
R ⁶ ₄ ▼ _-l or SiX _p (OR ⁷ ) _4-p (where X is Cl or
Br, R ⁶ and R ⁷ are each an alkyl group having 1 to 20 carbon atoms,
An aryl group or a cycloalkyl group having 3 to 20 carbon atoms, l
Or p is a number from 1 to 4) (component B) composed of a silicon halide represented by the formula (3) is reacted to precipitate a solid (hereinafter referred to as a solid product (I)), and III. I) is preliminarily polymerized with an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound to obtain a solid product (II). IV. The solid product (II) has the general formula TiX _q (OR ⁹ ) _4-q (wherein X is Cl or Br, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4) And / or VX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t (where X is Cl or Br, R ¹⁰ and R ¹¹ are Each is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and s is 1
(T of 3 is a number from 1 to 4) is characterized by reacting (component C) consisting of vanadyl halide or vanadium halide represented by a solid (hereinafter referred to as solid product (III)). Process for producing solid catalyst component for olefin polymerization. 2. A solid product (I), (II) or (II)
The method according to claim (1), wherein 0.01 to 500 g of α-olefin is reacted with 1 g of titanium atom in I).