JPH0745542B2 - Method for producing catalyst component for olefin polymerization - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a catalyst component for olefin polymerization. More specifically, the method for producing a catalyst component for an olefin polymerization, which is a catalyst component comprising a magnesium compound as a main supporting material and titanium halide as a supported component, which has improved storage stability, thermal stability and abrasion resistance. Regarding

[Technology of prior application and its problems]

Previously, the inventors of the present invention, in Japanese Patent Application No. 60-244499, a novel method for producing a solid catalyst component which gives an odorless olefin polymer having a high polymerization activity, a high stereoregulatory property and a narrow molecular weight distribution (hereinafter referred to as 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. Compared with the case where it is not performed, it becomes expensive, 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. Incidentally, it is a fact known 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 have 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 of does not substantially decrease in its catalytic activity even when the storage temperature is maintained at a temperature significantly higher than room temperature (hereinafter referred to as supernormal temperature) such as 40 ° C. 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 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 molecular weight. An object of the present invention is to provide a method for producing a catalyst component for olefin polymerization, which gives an odorless olefin polymer having a narrow distribution.

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 main 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) has the 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 respectively an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, l and p Is 1 to 4
A solid (hereinafter referred to as solid organism (I)) is precipitated by mixing and reacting the solid product (I) with an α-olefin having 2 or more carbon atoms in the presence of an organoaluminum compound. A solid product (II) is obtained by prepolymerization treatment, and IV. The solid product (II) is added to a titanium halide represented by the general formula TiX _q (OR ⁹ ) _4-q (where X is Cl Or B
r and B ³ are alkyl groups having 1 to 20 carbon atoms, aryl groups or cycloalkyl groups having 3 to 20 carbon atoms, and q is a number of 1 to 4) and / or the general formula VOX _s (OR ¹⁰ ). _3-s or VX _t (OR ¹¹ ) _4-t represented by vanadyl halide or vanadium halide (where 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, s is 1 to 3, and t is 1 to 4). (Component B) is reacted to give a solid (hereinafter referred to as solid product (III)
V. In any one or more of the above-mentioned steps I to IV, the aromatic polyvalent carboxylic acid ester is added to the component A or the solid product (I), (II) or (III). A method for producing a catalyst component for olefin polymerization, which comprises mixing and reacting.

(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 structure 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 and reacting components and in the presence or absence of the components in an inert hydrocarbon. The component has the general formula MgX _n (O
R ¹ ) is a magnesium halide represented by _2-n . Here, 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 of 0 to 2. Specifically, it is anhydrous magnesium dihalide, alkoxy magnesium halide and magnesium dialkoxide. More specifically, anhydrous magnesium chloride and anhydrous magnesium bromide can be used as the anhydrous magnesium dihalide. Anhydrous may include those containing trace amounts of water as much as commercial products commercially available as these "anhydrous" compounds.

As the magnesium alkoxide, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium bis-2-ethylhexanoxide, magnesium dioctanoxide, magnesium diphenoxide, magnesium dicyclopropoxide, magnesium methoxy. Mention may be made of ethoxide, 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, anhydrous magnesium chloride, magnesium diethoxide, ethoxymagnesium 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-methylhexyl 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 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, di-n-octyl phthalate, didecyl phthalate, diendyl phthalate, phthalate. 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 benzenetetracarboxylic acid such as monomethyl prenitate, diethyl prenitate, tripropyl prenitate, tetrabutyl prenitate, diethylbutyl prenitate, dibutyl merophanate, 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. Examples of naphthalene polyvalent carboxylic acid esters include naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, and naphthalene pentacarboxylic acid monoesters.
Di, tri, tetra and pentaesters can be used.

The following methods may be mentioned as specific methods for mixing and dissolving the components and in the presence or absence of the components in an inert hydrocarbon solvent. That is, in the presence or absence of the components, the components and are mixed in an inert hydrocarbon solvent in any order, and the suspension is heated with stirring. The components and are stirred in the inert hydrocarbon solvent. While heating and adding the ingredients to the solution, heating the ingredients and in an inert hydrocarbon solvent with stirring, then adding the ingredients, or alternatively, heating the ingredients and in an inert hydrocarbon solvent with stirring, then Add 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.

When the components are used, the amount used is 0.01 to 0.8 mol, preferably 0.03 to 0.7 mol, per 1 mol of the component. Thus, Step I provides (Component A).

Next, Stage II will be described.

The component is represented by the general formula SiX _l ▲ R ⁷ ₄ ▼ _-l or SiX _p (OR ⁸ ) _4-p
Is a halogenated silicon. Where X is Cl
Alternatively, Br, R ⁷ and R ⁸ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and 1 or p is a number 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,
For example, dibutyl silicon dichloride and triethyl silicon chloride, as SiX _p (OR ⁸ ) _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.

Then, in the presence or absence of the component (component A)
And the reaction of ingredients. The solid product (I) is obtained by the reaction of (component A) with the component. This reaction is carried out in the presence or absence of components a. Add a component to (Component A), b. (Component A) is added to the ingredients, or c. It can be carried out by a method such as adding a part of the components to (component A) and then adding the remaining components of the components to it or adding it to the remaining components of the components.

The use ratios of (Component A) and components are as follows. The amount of the component used is 0.1 to 50 mol, preferably 1 to 20 mol, based on 1 mol of the component (Component A) as a raw material. When the component is used, the amount used is 0.01 to 0.8 mol, preferably 0.03 to 0.7 mol, per 1 mol of the component. These components may be used at one time or may be used in several stages. The reaction temperature between the component (A) and the component in the presence or absence of the component is -40 to +18.
It is 0 ° C., preferably −20 to + 150 ° C., and the reaction time is 5 minutes to 6 hours, preferably 10 minutes to 5 hours in each step at a reaction pressure of 0 to 5 kg / cm ² G. The solid product (I) is precipitated by the reaction of stage II. The solid product (I) may be subsequently reacted in the next step, but it is extremely preferable to wash it with the inert hydrocarbon solvent as described above.

Next, step III will be described. At this stage, the previous stage II
The solid product (I) obtained in (1) is brought into contact with 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 organic aluminum compound, a general formula described later
A compound represented by AlX _r ▲ R ¹⁴ ₃ ▼ _-r can be used. Examples of the α-olefin having 2 or more carbon atoms include ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1,4-methylpentene-1 and 3
-In addition to methylpentene-1, butadiene, isoprene,
Mention may be made of 1,4-pentadiene and methyl-1,4-hexadiene. Inert hydrocarbon solvents can include hexane, heptane, nonane, decane and kerosene. 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. An α-olefin is supplied after suspending the solid product (I) in an inert hydrocarbon solvent in which an organoaluminum compound is dissolved, or an inert hydrocarbon solvent solid in which an organoaluminum compound and an α-olefin are dissolved. The product (I) is added, and α-olefin is further supplied if necessary. The α-olefin is fed so that the amount of the olefin polymer 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 0.1 to 500 mol, preferably 0.5 to 100 mol, per 1 mol of titanium atom contained in the solid product (I). 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). Prepolymerization temperature is -20 ℃ to +5
The temperature is 0 ° C., preferably 0 to 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 thereof used is 0 to 2 mol, preferably 0 to 0.5 mol, per mol of the organoaluminum compound. As a result of the prepolymerization treatment, the solid product (I) is covered with the olefin polymer. The object to be treated is washed with the above-mentioned inert hydrocarbon solvent until no organoaluminum compound is detected in the filtrate. Thus the solid product (I
I) is obtained.

Next, step IV will be described.

The component (B) which is reacted with the solid product (II) consists of components and / or. Ingredients are represented by the general formula TiX _q (OR ⁹ ) _4-q
It is a titanium halide represented by. 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 1 to
It is a number of four. 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 Phenoxytitanium, dicyclohexoxytitanium dichloride, diethoxytitanium dibromide, dibutoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide and Examples include triphenoxy titanium bromide Door can be. 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 IV, instead of the one produced by the above reaction, It is also possible to use mixtures of tetrahalogenated titanium and orthotitanate. 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 B) in the presence or absence of components will be described. This step IV reaction is carried out by adding (Component B) to the solid product (II) suspended in the described inert hydrocarbon solvent in the presence or absence of the components, or forming a solid product in (Component B). Object (II)
Alternatively, it can be carried out by a method such as adding a suspension solution thereof. The amount of the component constituting (Component B) or used is 1 to 100 mol, preferably 3 to 50 mol, per 1 mol of the component which is a constituent raw material of the solid product (II). When the components are used, the amount used is 0.01 to 0.8 mol, preferably 0.03 to 0.7 mol, per 1 mol of the component. Since the components can be used in at least any one or all of the stages I to IV, the total amount of the components used is 0.
The amount is 01 to 0.8 mol, preferably 0.05 to 0.7 mol. The reaction temperature of the solid product (II) and (component B) in the presence or absence of the components is 40 to 200 ° C, preferably 50 to 150.
The reaction time is 5 minutes to 6 hours, preferably 10 minutes to 5 hours under a pressure of 0 to 5 kg / cm ² . 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. In addition,
As mentioned above, the step V reaction is carried out in any one or more of steps I to IV and is not a separate step.

It is also possible to further pre-polymerize the solid product (III) before producing the olefin polymer 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 the treatment is not used for the regular polymerization of the olefin.

Next, a method for producing an olefin polymer will be described. The solid product (III) can be used as a catalyst for producing an α-olefin polymer 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. Here, X is Cl, R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 to 20 carbon atoms.
Is a cycloalkyl group of and r is a number from 0 to 2. Specifically, triethylaluminum, tri-n-propylaluminum, tri-i-butylaluminum, tricyclopentylaluminum, tricyclohexylaluminum, dimethylaluminium chloride, diethylaluminum chloride, di-n-butylaluminum choroid, ethylaluminum 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.

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, and u is 0 to 3 numbers.

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, dimethyldibenzyl Kishishiran, 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 methylethylphenylphenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldiethoxysilane, methylbenzyl Dimethoxysilane,
Dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane and trimethylethoxysilane are preferable.

The solid product (III), the organoaluminum compound and the organosilicon compound component may be combined by a method in which the solid product (III), the organoaluminum compound component and the organosilicon compound component are independently supplied to the polymerization vessel. The mixture of the silicon compound component and the solid product (III) may be independently fed to the polymerization vessel, or the mixture of the solid product (III), the organoaluminum compound and the organosilicon compound component may be fed to the polymerization vessel. 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 and is -50 to + 50 ° C,
The temperature is 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 10 to 1000 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.

Using the solid product (III) as a catalyst component for olefin polymerization according to the present invention, a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound, an olefin polymer is obtained by using an α-olefin having 3 or more carbon atoms. To manufacture. 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 other α-olefins having 2 or more carbon atoms
It also includes copolymerization with one or more kinds. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-pentadiene, and methyl-1,4-hexadiene, in addition to the α-olefin having 3 or more carbon atoms described above. The amount of those other α-olefins used depends on the copolymer obtained by copolymerization.
The amount is 50% by weight or less. 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, hexane, heptane, nonane,
An inert hydrocarbon solvent such as 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 in the polymerization vessel by catalyzing the catalyst and α-olefin. 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
It is 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 above-mentioned production or storage of the olefin polymerization catalyst, preparation of the catalyst and production of the polymer must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases, under an atmosphere of a monomer or under vacuum conditions. But you can do it too.

The effects obtained by the present invention are as follows.

The catalyst component for olefin polymerization according to the present invention is excellent in storage stability and thermal stability. It is an industrially extremely important iron that it can be stably stored for a long 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.

Furthermore, the 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 means preventing the formation of finely divided catalyst and thus 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 odorless olefin polymer having a high stereoregularity, a narrow molecular weight distribution.

The present invention will be described below with reference to Examples and Comparative 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 homogeneous solution was heated to 70 ° C., 1.8 g of diisobutyl furarate was added with stirring, and after 1 hour, 52 g of silicon tetrachloride was added to 2.5 g.
The mixture was added dropwise over a period of time to precipitate a solid, which 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 3.6% by weight (hereinafter referred to as%). 500 ml of hexane containing 41 mmol of triethylaluminum in which the total amount of the solid product (I) was cooled to 10 ° C.
Ethylene was introduced into the suspension with stirring for 1 hour at the same temperature so that the polymer yield was 1.0 g-polymer / g-solid product (I). The solid product (II) was obtained by washing with hexane until no triethylaluminum was detected in the filtrate. The total amount of the solid product (II) was 1,
After mixing with 50 ml of titanium tetrachloride dissolved in 50 ml of 2-dichloroethane, 1.8 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C for 2 hours while stirring, and then the liquid phase portion was decanted at the same temperature. Except again, 1,2
-Add 50 ml of dichloroethane and 50 ml of titanium tetrachloride,
The mixture was stirred at 100 ° C for 2 hours, washed with hexane and dried to give a solid product (III). The solid product (III) has a particle shape close to that of a sphere, with Ti 1.1% and polyethylene 61.0.
%.

(2) Production of olefin polymer In a nitrogen-substituted stainless reactor with an internal volume of 3 and equipped with a multistage stirrer, 2 mmol of triethylaluminum, 0.3 mmol of diphenyldimethoxysilane, and 38.6 mg of solid product (III)
And after adding 0.8 hydrogen, the total pressure at 70 ℃ is 22kg / cm
Polymerization was carried out for 2 hours while continuously introducing propylene to ² G. Then, unreacted propylene was discharged to obtain 242 g of powdered polypropylene. The particle shape of the polypropylene was close to a sphere, the bulk density was 0.40, the odor of MFR 5.4 was not recognized, and it was ▲ ▼ / ▲ ▼ 4.5, and the boiling heptane extraction residual ratio (6 hours extraction) 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 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 (using 251 mg of a solid product (III), (1) of Example 4) and an attrition resistance test were conducted in the same manner except that ethylene was introduced at 15 ° C. for 3 hours. Example 2 (2)) was 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 an olefin polymer (using 15 mg of a solid product (III) equivalent, Comparative Example 1 (1)) and an attrition resistance test (Comparative Example 1 (2)) were carried out.

Comparative Examples 2 to 3 The solid product (III) obtained in Comparative Example 1 was used in a nitrogen atmosphere 4
It was stored at 0 ° C., and after 3 months (Comparative Example 2) and 6 months (Comparative Example 3), the solid product (III) was replaced by 38.6 mg of the solid product (III) in Example 1 (2). 15 equivalents
An olefin polymer was produced in the same manner except that mg was used.

Example 5 Solid product (I) 10 obtained in the same manner as in (1) of Example 1.
Hexane 1 containing 75 mmol of triethylaluminum and 12 mmol of phenyltriethoxysilane cooled to 20 ° C.
Propylene was introduced into the suspension for 1.5 hours at the same temperature so that the polymer yield was 1.0 g-polymer / g-solid product (II) while stirring. After washing with hexane to obtain a solid product (II), preparation of a solid catalyst component, production of an olefin polymer ((1) of Example 5 and abrasion resistance test (implementation) were carried out in the same manner as in Example 1. (2) of Example 5)
I went.

Example 6 In a stainless steel flask, 50 ml of nonane, 4.8 g of anhydrous magnesium chloride, 14.8 g of ethyl orthotitanate and 16.3 g of n-octanol were mixed and stirred at 110 ° C.
And heated for 2 hours to form a uniform solution. The solution was heated to 70 ° C., 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 obtain a solid product (I). The Ti content of the solid product (I) was 3.2%.
The total amount of the solid product (I) was suspended in hexane 1 containing 33 mmol of triethylaluminum and 8 mmol of methyl toluate cooled to 15 ° C., and the polymer yield in the suspension was 5.0 g-at the same temperature while stirring. Propylene was introduced for 2.5 hours to give a polymer / g-solid product (I). The solid product (II) was washed with hexane to obtain a solid product (II), which was mixed with 100 ml of titanium tetrachloride, followed by addition of 2.2 g of di-n-butyl phthalate, and the mixture was heated to 110 ° C. with stirring. 1.5
After reacting for a period of time, the liquid phase part was removed at the same temperature, 100 ml of titanium tetrachloride was added again, the mixture was stirred at 100 ° C. for 2 hours, and then washed with hexane to obtain a solid product (III). The solid product (III) has a particle shape close to a sphere, and Ti 0.
It contained 25% and 88.7% polypropylene. Production of an olefin polymer using the solid product (III) in the same manner as in Example 1 (use of 133 mg of the solid product (III), Example 6)
(1)) and the abrasion resistance test ((2) of Example 6). The polypropylene had a particle shape close to a sphere, had a bulk density of 0.38, and had no MFR 5.0 odor.
▼ / ▲ ▼ 4.8, boiling heptane extraction residual rate 97.8
%Met.

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, production of olefin polymer (using 15 mg of solid product (III) equivalent, Comparative Example 4 (1)) and abrasion resistance test (Comparative Example 4)
(2)) was performed.

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

Comparative Example 5 An olefin polymer 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 catalyst component of the present invention and a process for producing an olefin polymer using the catalyst component.

Claims (2)

[Claims] 1. A method for producing an olefin polymerization catalyst component comprising a titanium halide, vanadyl halide or vanadium halide supported on a carrier, the main component of which is a Mg compound precipitated from a solution state. 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) has the 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 respectively an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, l and p Is 1 to 4
Of the α-olefin having a carbon number of 2 or more in the presence of an organoaluminum compound, to precipitate a solid (hereinafter referred to as a solid product (I)) by a mixed reaction. To obtain a solid product (II), IV. The solid product (II) contains titanium halide represented by the general formula TiX _q (OR ⁹ ) _4-q (where X is Cl or B
r and B ⁹ are alkyl groups having 1 to 20 carbon atoms, aryl groups or cycloalkyl groups having 3 to 20 carbon atoms, and q is a number of 1 to 4) and / or the general formula VOX _s (OR ¹⁰ ). _3-s or VX _t (OR ¹¹ ) _4-t represented by vanadyl halide or vanadium halide (where 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, s is 1 to 3, and t is 1 to 4). (Component B) is reacted to give a solid (hereinafter referred to as solid product (III)
V. In any one or more of the above-mentioned steps I to IV, the aromatic polyvalent carboxylic acid ester is added to the component A or the solid product (I), (II) or (III). A method for producing a catalyst component for olefin polymerization, which comprises mixing and reacting. 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.