JPH0745541B2 - Method for producing solid catalyst component for producing polyolefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a solid catalyst component for producing a polyolefin. More specifically, the catalyst component comprising a magnesium compound as a main supporting material and titanium halide or the like as a supported component, which is a solid catalyst component for polyolefin production having improved storage stability, thermal stability and abrasion resistance Regarding manufacturing method.

[Technology of prior application and its problems]

Previously, the inventors of the present invention, in Japanese Patent Application No. 60-244500, a novel method for producing a solid catalyst component which gives an odorless olefin polymer having high polymerization activity, high stereoregularity and a narrow molecular weight distribution (hereinafter referred to as the prior application. (Referred to as “catalyst manufacturing method”).

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 when the solid catalyst component is produced on a large scale. There is a problem in that the powder is easily milled in the manufacturing apparatus and a fine powder solid catalyst component is produced.

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 proportion of fine powders of olefin polymers leads to unfavorable consequences with regard to handling and quality uniformity after the production 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 were studying the above problems,
In the catalyst production method of the prior application, when the solid product (I) precipitated from the solution state is polymerized with a small amount of α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound, the final product obtained is obtained. The solid product does not substantially deteriorate in its catalytic activity even when the storage temperature is maintained at a temperature significantly higher than room temperature such as 40 ° C. (hereinafter referred to as ultra-normal temperature), and the solid catalyst component is produced. The present invention has been accomplished by finding the fact that the above-mentioned fine powder is hardly generated at the time, or at the time of subsequent handling or use (Note. Pre-activation or polymerization). Incidentally, the pre-polymerization treatment is performed on the solid product (I), that is, the so-called pre-treatment of the α-olefin treatment on the combination (catalyst) of the final solid carrying the titanium compound and the organoaluminum compound. Activation has a different technical significance. The solid product (I) has the polymerization activity because the product note 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, to improve storage stability, thermal stability and abrasion resistance, and to have high polymerization activity and high stereoregularity. And a method for producing a catalyst component for olefin polymerization, which gives an odorless polyolefin having a narrow molecular weight distribution.

[Constitution / Effect of Invention]

 The present invention has the following configurations.

(1) In a method for producing a catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose major component is a Mg compound precipitated from a solution state, I. General formula MgX _n A magnesium halide represented by (OR ¹ ) _2-n (wherein X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n Is a number from 0 to 2), the general formula Ti
Orthotitanate represented by (OR ² ) ₄ and / or polytitanate represented by the general formula R ³ O—Ti (OR ⁴ ) (OR ⁵ ) _m O—R ⁶ (here, R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ 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 2
20)), and a saturated or unsaturated monohydric or polyhydric alcohol having 1 to 20 carbon atoms in an inert hydrocarbon solvent and reacted and dissolved to obtain (Component A), II. (Component A) is an aliphatic or aromatic monocarboxylic acid ester having 2 to 24 carbon atoms and a general formula SiX _l ▲
R ⁷ ₄ ▼ _-l or SiX _p (OR ⁸ ) _4-p (wherein X is Cl or Br, R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 to 20 carbon atoms) A cycloalkyl group, and 1 and p are numbers from 1 to 4) (component B) consisting of a silicon halide represented by the formula (1) is reacted to precipitate a solid I (hereinafter referred to as a solid product (I)), III. The solid product (I) is prepolymerized with a small amount of an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound to obtain a solid product (II), IV. ) In 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 a titanium halide represented by the general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t (wherein X is Cl or Br, R ¹⁰ and R ¹¹ are each 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
The solid (hereinafter referred to as the solid product (III)) is obtained by reacting (component C) composed of vanadyl halide or vanadium halide represented by 3 and t is a number of 1 to 4). Production of a polyolefin characterized by mixing an aromatic carboxylic acid ester with component A or solid product (I), (II) or (III) in any one or more of steps I to IV and reacting them. For producing solid catalyst components for automobiles.

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

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 mixing the components and and in an inert hydrocarbon and reacting and dissolving them. The component is a magnesium halide represented by the general formula MgX _n (OR ¹ ) _2-n . Here, X is Cl or Br, R ¹ has ¹ carbon atom
Is an alkyl group having 20 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 2. Specifically, they are magnesium dihalide, alkoxy magnesium halide and magnesium dialkoxide.
More specifically, magnesium chloride and anhydrous magnesium bromide can be used as the magnesium dihalide.

As the magnesium alkoxide, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium di-2-ethylhexanoxide, magnesium dioctanoxide, magnesium diphenoxide, magnesium dicyclopropoxide, magnesium Mention may be made of methoxyethoxide, magnesium ethoxybutoxide, magnesium ethoxyphenoxide and the like.

Examples of the alkoxy magnesium halides include methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, 2-ethylhexanoxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium bromide, phenoxy magnesium bromide and octanoxy magnesium bromide. be able to.
Among these compounds, magnesium chloride, magnesium diethoxide, ethoxy magnesium chloride and the like are preferable.

The component is a titanate ester. Examples of the titanic acid ester include an orthotitanic acid ester represented by Ti (OR ² ) ₄ and a polytitanic acid ester represented by R ³ O—Ti (OR ⁴ ) (OR ⁵ ) _m O—R ⁶ . Where R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ 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 carbon, halogenated hydrocarbons such as 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 with stirring in an inert hydrocarbon solvent, and the components are added to the solution. And the ingredients and are heated in an inert hydrocarbon solvent with stirring and then the ingredients are added, or the ingredients and are heated in an inert hydrocarbon solvent with stirring and then the ingredients are added.

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.

On the other hand, if the amounts of the components and used are too small, the components do not dissolve in the inert hydrocarbon solvent, the solid catalyst component has an amorphous shape, and a spherical or near spherical particle-shaped polymer cannot be obtained. 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. Examples of the organic acid ester include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl propionate,
N-propyl propionate, i-butyl propionate,
Use aliphatic carboxylic acid esters such as ethyl acetate and phenyl acetate, and aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate and phenyl anisate. You can

The component has the general formula SiX _l ▲ R ⁷ 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 alkyl groups having 1 to 20 carbon atoms, aryl groups or cycloalkyl groups having 3 to 20 carbon atoms, and 1 and p are numbers of 1 to 4. Specifically, SiX _l
▲ R ⁷ 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,
Dibutyl silicon dichloride and triethyl silicon chloride, such 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, diphenyl 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. It can be carried out by a method of adding a part of (component B) to (component A) and then adding the remaining component of (component B) or adding it to the remaining component of (component B). .

Specifically, for example, there are the following methods. That is, the component A is reacted with the component and then the components are reacted to precipitate the solid product (I). The components and are reacted simultaneously to precipitate the solid product (I). After reacting the components to deposit a solid, the components are 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 is mixed with or reacted with (Component A). (Component A) or a mixture or reaction product of (Component A) and 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), it is usually preferable to add the component to (Component A), but the component may be added to (Component A) or (Component A) may be added to the component. it can. Since the particle shape of the solid product (II) is governed by the particle shape of the solid product (I), the particle shape can be controlled by using a component and (component A) or a mixture of component (A) and a component or a reactant. The reaction of 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, preferably 0.1 to 0.6 mol, and the amount of the component used is 0.1 to 50 mol, preferably 1 to 1 mol with respect to 1 mol of the component (Component A) as a raw material. 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 BS) is -40 to +180.
C., preferably −20 to + 150 ° C., and the reaction time for each step is 5 minutes to 6 hours, preferably 10 minutes to 5 hours. The solid product (I) precipitated by the reaction of (Component A) and (Component B) may be subjected to the subsequent reaction step, but it should be washed with the inert hydrocarbon solvent described above. Is preferred. Thus, a spherical or near spherical solid product (I) 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 ¹⁴ 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 of contacting the solid product (I) with the α-olefin to prepolymerize, 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 to the inert hydrocarbon solvent in which the organoaluminum compound and the α-olefin are dissolved. For example, the solid product (I) is added, and α-olefin is further supplied if necessary.

The polyolefin which is prepolymerized per 1 g of the solid product (I) is
Α1 to be 0.001 to 1000 g, preferably 0.01 to 500 g
Supply olefin. The amount of organic aluminum used is
Based on 1 mol of titanium atom contained in the solid product (I)
It is 0.1 to 500 mol, preferably 0.5 to 100 mol. The amount of the inert hydrocarbon solvent used is 0 to 1 g of the solid product (I).
It is 1000 ml, preferably 5-500 ml. The temperature during prepolymerization is -20 to + 50 ° C, preferably 0 to 30 ° C, and the time is 1
Minutes 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 thereof used is 0 to 2 mol, preferably 0 to 0.5 mol, per mol of the organoaluminum compound. The solid product (I) is covered with polyolefin. Wash with the above-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.

(Component C) consists of and / or. The component is a titanium halide represented by the general formula TiX _q (OR ⁹ ) _4-q . Here, 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. Specifically, titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, hexoxytitanium trichloride, octoxytitanium trichloride, phenoxytitanium trichloride, trititanium trichloride. Cyclohexoxy titanium chloride, ethoxy titanium tribromide, butoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dibutoxy titanium dichloride, dioctoxy titanium dichloride, dichloride dichloride Phenoxy titanium, dicyclohexoxy titanium dichloride, diethoxy titanium dibromide, dibutoxy titanium dibromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, triethoxy titanium bromide and Examples include triphenoxy titanium bromide It is possible. Titanium halides other than titanium tetrachloride or titanium tetrabromide can be produced by the reaction of titanium tetrahalide with orthotitanate,
A mixture of titanium tetrahalide and orthotitanate can also be used in the Step IV reaction instead of the one produced by the above reaction. 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
, T is a number from 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 tetrachloride, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, tris Phenoxy vanadium chloride, cyclohexoxy vanadium trichloride, ethoxy vanadium tribromide, dimethoxy vanadium dichloride, diethoxy vanadium dichloride, dibutoxy vanadium dichloride, diphenoxy vanadium dichloride, diethoxy vanadium dibromide, triethoxy vanadium chloride , Triphenoxy vanadium chloride, triethoxy vanadium bromide and the like. 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.

The component is an aromatic polycarboxylic acid ester. Examples of the aromatic polyvalent carboxylic acid ester include benzene polyvalent carboxylic acid ester and naphthalene polyvalent carboxylic acid ester. Specifically, as the benzene polycarboxylic acid ester, monomethyl phthalate, dimethyl phthalate, monoethyl phthalate, diethyl phthalate, dipropyl phthalate, mono-n-butyl phthalate,
Di-n-butyl phthalate, monoisobutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, n-octyl phthalate, didecyl phthalate, dibenzyl phthalate, phthalic acid Diphenyl, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-isophthalate
Mono- and diesters of benzeldicarboxylic acid such as ethylhexyl, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, dibenzyl terephthalate and diphenyl terephthalate, monobutyl hemimelate, dibutyl hemimelate, tributyl hemimelate, trimellit. Mono-, di- and triesters of benzene tricarboxylic acid such as monoethyl acid acid, dipropyl trimellitate, tributyl trimellitate, diethyl trimesate, tributyl trimesate and tri-2-ethylhexyl trimesate,
Mono-, di-, tri- and tetra-esters of benzene tetracarboxylic acid such as mono-methyl prenitate, diethyl prenitate, tripropyl prenitate, tetrabutyl prenitate, diethyl dibutyl prenitate, dibutyl merophane, tetrabutyl pyromelliticate and dimethyldipropyl pyromelliticate. It is possible to use mono-, di-, tri-, tetra-, penta- and hexa-esters of benzene pentacarboxylic acid and mellitic acid. Further, as the naphthalene polyvalent carboxylic acid ester, mono-, di-, tri-, tetra- and penta-esters of naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid and naphthalene pentacarboxylic acid can be used.

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

Specifically, for example, there are the following methods. That is, the solid product (II), in an inert hydrocarbon solvent,
Ingredients and / or ingredients are added simultaneously and allowed to react. , In an inert hydrocarbon solvent, and / or
Alternatively, and after adding the components, the solid product (II) is added and reacted, and the liquid component and / or the solid product (II) is added and then the components are added and reacted.
Examples of the method include adding a liquid component and / or a component, and then adding the solid product (II) to the reaction, or combining two or more of the above.

The amount of the component or used is 1 to 100 with respect to 1 mol of the magnesium compound which is a constituent raw material of the solid product (II).
Mol, preferably 3 to 50 mol.
It is 0.01 to 0.8 mol, preferably 0.03 to 0.7 mol. These components may be used at one time or may be used in several stages.

The reaction temperature of the solid product (II) and (component C) is 40 to 200.
℃, preferably 50 ~ 150 ℃, reaction time 5 minutes ~ 6 hours,
It is preferably 10 minutes to 5 hours. After the reaction, the solid is separated by another method or a decantation method and then washed with an inert hydrocarbon solvent to remove unreacted substances or 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) can be dried and stored as a powder, or can be stored by suspending it in the above-mentioned inert hydrocarbon solvent. As mentioned above, the reaction of Step V is carried out in any one or more of Steps I to IV and is not an independent step.

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

Next, the polyolefin production method will be described. The solid product (III) can be used as a catalyst for producing a polyolefin by combining it as a solid catalyst component with an organoaluminum compound and an organosilicon compound component having a Si—O—C bond. As the organoaluminum compound to be combined, a compound represented by AlX _r ▲ R ¹⁴ ₃ ▼ _-r can be used. Where X is Cl and R ¹⁴ has 1 to 20 carbon atoms.
Is an alkyl group, 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, trichlorohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum chloride,
Examples thereof include ethylaluminum sesquichloride and ethylaluminum dichloride. 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 three kinds of organoaluminum compounds such as aluminum and ell aluminum sesquichloride.

The organosilicon compound component has the general formula ▲ R ¹² _u ▼ Si (O
A compound represented by R ¹³ ) _4-u can be used.
Here, R ¹² and R ¹³ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
u is a number from 0 to 3.

Specifically, methyl silicate, ethyl silicate, butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methylethoxydimethoxysilane, methylphenoxydimethoxysilane, methylmethoxy. Ethoxyphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriphenoxysilane,
Ethyltribenzyloxysilane, ethylethoxydimethoxysilane, ethylmethoxydiethoxysilane, ethylphenoxydimethoxysilane, ethylmethoxyethoxyphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylphenoxy Dimethoxysilane, benzylmethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, phenylmethoxyethoxyphenoxysilane, dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyldiphenoxysilane, dimethyldiben Rokishishiran, dimethyl methoxy silane, dimethyl-methoxyphenoxy silane,
Dimethylethoxyphenoxysilane, methylethyldimethoxysilane, methylethyldiphenoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiphenoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, phenylbenzyldimethoxysilane, methyl Cyclopropyldimethoxysilane, methylvinyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylbenzyloxysilane, triethylmethoxysilane, triethylethoxysilane, triethylphenoxysilane,
Triphenylmethoxysilane, tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, diethylmethylmethoxysilane, diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxy Examples thereof include silane and ethylethylphenylphenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, Methylethyldiethoxysilane, methylphenyldiethoxysilane, methylbenzyldimethoxysilane,
Dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane are preferred. As a combination method of solid product (III), organoaluminum compound and organosilicon compound component Is a solid product (III), an organoaluminum compound and an organosilicon compound component that are independently fed to a polymerization vessel, and a mixture of an organoaluminum compound and an organosilicon compound component and a solid product (III) are independently fed to a polymerization vessel. A solid product (III), a mixture of an organoaluminum compound and an organosilicon compound component, a mixture of components is fed to a polymerization vessel,
Etc., 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 when mixing prior to feeding to the polymerizer, such as and, is-
50 to + 50 ° C, preferably -30 to + 30 ° C, time is 5 minutes to
It is 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is 10 to 100 mol, preferably 50 to 500 mol, per 1 mol of titanium atom contained in the solid product (III) as the solid catalyst component. The amount of the organosilicon compound used is 0.01 to 2 mol, preferably 0.05 to 1 mol, per 1 mol of the organoaluminum compound. When a mixed organoaluminum compound or a mixed organosilicon compound 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
I), a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound is used to produce a polyolefin using an α-olefin having 3 or more carbon atoms. Examples of the α-olefin 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 can be used. In the polymerization of these α-olefins, not only homopolymerization but also one or two other α-olefins having 2 or more carbon atoms
It also includes copolymerization with one or more species. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1, in addition to the α-olefin having 3 or more carbon atoms described above.
4-pentadiene and methyl-1,4-hexadiene can be mentioned. The amount of those other α-olefins used is such that the copolymer obtained by the copolymerization will contain less than 50% by weight. The polymerization can be carried out in the liquid phase or the gas phase. When carrying out the polymerization in the liquid phase, for example, an inert hydrocarbon solvent such as hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may also be used as the reaction medium. it can. 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.
The polymerization temperature is 40 to 200 ° C, preferably 50 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 components 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, also in a monomer atmosphere or in a vacuum condition. be able to.

The effects obtained by the present invention are as follows.

The solid catalyst component for producing polyolefin according to the present invention is excellent in storage stability and thermal stability. Stable storage is extremely important industrially for a long period of time regardless of high and low outside temperatures. The storage can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Furthermore, the solid catalyst component according to the present invention is excellent in abrasion resistance. The component is less susceptible to attrition during use, i.e., during the polyolefin manufacturing process as well as during the catalyst manufacturing process. This means preventing the formation of finely divided catalyst and thus the formation of finely divided polymer. As a result,
It was possible to solve the entrainment problem that is likely to occur during the production of polyolefins in the gas phase polymerization process.

Another advantage of the present invention is that the polymerization activity is extremely high and removal of residual catalyst in the polymer is not necessary. In addition, it is possible to produce an odorless polyolefin having high stereoregularity, a narrow molecular weight distribution.

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, 3.5 g of ethyl p-toluate was added, and the mixture was heated to 70 ° C. for 1 hour, and subsequently 52 g of silicon tetrachloride was added dropwise over 2.5 hours with stirring to precipitate a solid.
It was further heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (I). The Ti content of the solid product (I) was 3.0% by weight (hereinafter referred to as%). The total amount of the solid product (I) was suspended in 500 ml of hexane containing 34 mmol of triethylaluminum cooled to 10 ° C., and the polymer yield in the suspension was 1.0 g-polymer / g-solid production in the suspension at the same temperature while stirring. Ethylene was introduced for 1 hour so that the product (I) was obtained. 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, subsequently 2.8 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. At the same temperature, the liquid phase part was removed by decantation, 50 ml of 1,2-dichloroethane and 50 ml of titanium tetrachloride were added again, and the mixture was stirred at 100 ° C for 2 hours, washed with hexane and dried to give a solid product (III). did.
The solid product (III) has a particle shape close to a sphere,
It contained 0.86% and polyethylene 61.0%.

(2) Production of polyolefin In a reactor made of stainless steel with a multi-stage stirrer having an internal volume of 3 and which was replaced with nitrogen, 2 mmol of triethylaluminum, 0.3 mmol of diphenyldimethoxysilane, and a solid product (II)
After adding 38.6 mg of hydrogen and 0.7 of hydrogen, 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 179 g of powdery polypropylene. The particle shape of the polypropylene is close to spherical, MFR5.0, bulk density
0.40, no odor was observed ▲ ▼ / ▲ ▼ 4.6, and the boiling heptane extraction residual ratio (6 hours) was 98.0%.

(3) Attrition resistance test In a nitrogen atmosphere, using a magnet drive type circulation pump (Iwaki magnet pump MD-10 type),
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 polyolefin was treated in the same manner as in Example 1 (2). Was manufactured.

Examples 2 to 3 The solid product (III) obtained in Example 1 was used in a nitrogen atmosphere 4
After storing at 0 ° C., a polyolefin was produced in the same manner as in (2) of Example 1 after 3 months (Example 2) and 6 months (Example 3).

Example 4 When the solid product (II) was obtained from the solid product (I) in (1) of Example 1, the polymer yield was 10 g-polymer / g.
-Preparation of the solid catalyst component in the same manner except that ethylene is introduced for 3 hours at 15 ° C so as to give the solid product (I),
The production of polyolefin ((1) of Example 4) and the abrasion resistance test ((2) of Example 4) were performed.

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 a polyolefin (using 15 mg of a solid product (III) equivalent, Comparative Example 1 (1)) and an abrasion resistance test (Comparative Example 1 (2)) were carried out.

Comparative Examples 2 to 3 The solid product (III) equivalent product 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 were obtained. In (2) of 1 above, the solid product (III) equivalent was replaced with 38.6 mg of the solid product (III).
A polyolefin was produced in the same manner except that 15 mg was used.

Example 5 Solid product (I) 10 obtained in the same manner as in (1) of Example 1.
Hexane 1 containing 63 mmol of triethylaluminum and 10 mmol of phenyltriethoxysilane cooled to 20 ° C.
Propylene was introduced into the suspension for 1.5 hours at the same temperature with stirring so that the polymer yield was 1.0 g-polymer / g-solid product (I). After washing with hexane to obtain a solid product (II), preparation of a solid catalyst component, production of a polyolefin ((1) of Example 5) and an abrasion resistance test (Example) were carried out in the same manner as in Example 1. 5 (2))) was performed.

Example 6 In a stainless steel flask, 50 ml of nonane, 4.8 g of anhydrous magnesium, 14.8 g of ethyl orthotitanate and n
-Mix 16.3g octanol and stir to 110 ° C for 2
Heated for a period of time to give a homogeneous solution. The solution was heated to 70 ° C., 3.2 g of ethyl benzoate was added and dissolved, and then 65 g of phenylsilicon trichloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred at 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (I). The Ti content of the solid product (I) was 2.5%. Total amount of the solid product (I) cooled to 15 ° C. triethylaluminum 29
Hexane containing 1 mmol and 3 mmol methyl toluate 1
Propylene was introduced into the suspension at the same temperature for 2.5 hours with stirring so that the polymer yield was 5.0 g-polymer / g-solid product (I). Washing with hexane gives a solid product (II), which is mixed with 100 ml of titanium tetrachloride, followed by di-n-phthalic acid.
After adding 2.2 g of butyl and reacting at 110 ° C for 1.5 hours with stirring, remove the liquid phase at the same temperature, add 100 ml of titanium tetrachloride again and stir at 100 ° C for 2 hours, then wash with hexane and dry. To give a solid product (III).

The solid product (III) has a particle shape close to a sphere, and T
It contained 0.20% i and 88.7% polypropylene. Using the solid product (III), polypropylene was produced in the same manner as in Example 1 (133 mg of the solid product (III) was used, (1) of Example 6) and the abrasion resistance test ((2) of Example 6). ))
I went. The polypropylene obtained in (1) of Example 6 has a particle shape close to a sphere, a bulk density of 0.39, and MFR4.
6, no odor, ▲ ▼ / ▲ ▼ 4.8,
The boiling heptane extraction residue rate was 97.7%.

Comparative Example 4 A solid product was obtained in the same manner as in Example 6 except that the whole amount of the solid product (I) obtained in the same manner as in Example 6 was used as the solid product (II) equivalent (the prepolymerization treatment was omitted). Preparation of polyolefin (use of 15 mg of solid product (III) equivalent,
The (1) of Comparative Example 4 and the abrasion resistance test ((2) of Comparative Example 4) were performed.

Example 7 The solid product (III) obtained in Example 6 was treated under a nitrogen atmosphere.
It was stored at 0 ° C., and after 6 months, a polyolefin was produced in the same manner as in Example 6.

Comparative Example 5 A polyolefin was produced (using 15 mg of the solid product (III) equivalent) in the same manner as in Example 7 except that the solid product (III) equivalent obtained in Comparative Example 4 was used.

[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 catalyst component for olefin polymerization in which titanium halide, vanadyl halide or vanadium halide is supported on a carrier comprising a Mg compound precipitated from a solution state as a main constituent, comprising the steps of I. Magnesium halide represented by MgX _n (OR ¹ ) _2-n (wherein X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms; , N is a number from 0 to 2), the general formula Ti
Orthotitanate represented by (OR ² ) ₄ and / or polytitanate represented by the general formula R ³ O—Ti (OR ⁴ ) (OR ⁵ ) _m O—R ⁶ (here, R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ 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 2
20)), and a saturated or unsaturated monohydric or polyhydric alcohol having 1 to 20 carbon atoms in an inert hydrocarbon solvent and reacted and dissolved to obtain (Component A), II. (Component A) is an aliphatic or aromatic monocarboxylic acid ester having 2 to 24 carbon atoms and a general formula SiX _l ▲
R ⁷ ₄ ▼ _-l or SiX _p (OR ⁸ ) _4-p (wherein X is Cl or Br, R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 to 20 carbon atoms) A cycloalkyl group, and 1 and p are numbers from 1 to 4) (component B) consisting of a silicon halide represented by the formula (1) is reacted to precipitate a solid I (hereinafter referred to as a solid product (I)), III. The solid product (I) is prepolymerized with a small amount of an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound to obtain a solid product (II), IV. ) In 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 a titanium halide represented by the general formula VOX _s (OR ¹⁰ ) _3-s or VX _t (OR ¹¹ ) _4-t (wherein X is Cl or Br, R ¹⁰ and R ¹¹ are each 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, where t is a number from 1 to 4) (component C) consisting of vanadyl halide or vanadium halide represented by the formula (3) is reacted to obtain a solid (hereinafter referred to as a solid product (III)). Polyolefin characterized by mixing and reacting component A or solid product (I), (II) or (III) with an aromatic carboxylic acid ester in any one or more of said stages I to IV Method for producing solid catalyst component for production. 2. 0.01 to 500 g of α based on 1 g of the solid product (I).
-The method according to claim (1) in which an olefin is reacted.