JPH0780954B2 - Titanium catalyst component for producing olefin polymer and method for producing the same - Google Patents

Description

The present invention relates to a titanium catalyst component for producing an olefin polymer and a method for producing the same. More specifically, the present invention relates to a titanium catalyst component for producing an olefin polymer, which is suitable as a transition metal compound catalyst component for producing a highly crystalline olefin polymer having excellent transparency, and a production method thereof.

[Conventional technology and its problems]

The crystalline olefin polymer such as crystalline polypropylene is
A so-called Ziegler-comprising a transition metal compound of group IV to VI and an organometallic compound of group I to III of the periodic table
It is well known that it can be obtained by polymerizing an olefin with a Natta catalyst, and a method for obtaining an olefin polymer having high polymerization activity and high stereoregularity has been pursued. Among them, titanium, gnesium, which show extremely high polymerization activity while maintaining high stereoregularity,
Recently, a method of producing an olefin polymer by polymerizing an olefin by using a catalyst containing a titanium-containing solid catalyst component containing a halogen and an electron donor, an organoaluminum compound, and an electron donor, has been studied vigorously in recent years. Has been done. (For example, JP-A-58-83,006, etc.) The present applicant has already made many proposals in this field, for example, JP-A-61-209,207 and JP-A-62-104,8.
No. 10, JP-A-62-104,811, JP-A-62-104,812, JP-A-62-104,813, etc., extremely high polymerization of an olefin polymer having a high stereoregularity and good particle shape. The method of obtaining with activity is disclosed.

However, although these improved methods have the advantages as described above, the obtained olefin polymer is translucent, which may impair the commercial value in the application field, and improvement of transparency is desired. Was there.

On the other hand, attempts have been made to improve the transparency of olefin polymers, such as aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22,740). There is a method of adding a nucleating agent such as) to polypropylene, but when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. ,
When a benzylidene sorbitol derivative is used,
Although some improvement was seen in transparency, there were problems such as strong odor during processing and bleeding (embossing) of additives.

In order to improve the above-mentioned problems when adding a nucleating agent, there is provided a method for carrying out multi-stage polymerization of styrene, pt-butylstyrene, allyltrimethylsilane and the like and a composition thereof (Japanese Patent Publication No. 62-1,738). JP-A-62-227,911, JP-A-63-15,803, JP-A-63-15,804, JP-A-63-68,648, etc.) have been proposed,
According to the method proposed by the present inventors, when polypropylene is produced, not only the polymerization activity of propylene is decreased in any method, but also a lumpy polymer is produced, so that industrial long-term continuous production is possible. This method cannot be used in a polymerization method, particularly in a gas phase polymerization method in which olefin polymerization is carried out in a gas phase. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

As a similar technique, a method of polymerizing propylene using the catalyst component obtained by adding a pt-butylstyrene polymer, an allyltrimethylsilane polymer or the like during the production of a transition metal catalyst component for propylene polymerization (JP-A-63-69,
No. 809) has been proposed, but the proposed method requires an additional step of producing a pt-butylstyrene polymer, an allyltrimethylsilane polymer, etc., and thus has an industrial disadvantage. In addition to the above-mentioned prior art, there was a problem of void formation in the film.

The present inventors, when producing an olefin polymer having improved transparency, have keenly studied a method for solving the problems such as the generation of a bulk polymer and the occurrence of voids in a film due to poor dispersion, which the conventional technology has. did.

As a result, a titanium catalyst component containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer was found by a specific method, and when a catalyst obtained by combining the titanium catalyst component with an organoaluminum compound was used, Is a solution to the problems in the production of olefin polymers of the prior art as described above, and an olefin polymer having excellent transparency and crystallinity, which has good dispersibility and very few voids. Not
The present invention has been accomplished by knowing that there is a remarkable effect also on the storage stability of the titanium catalyst component at a high temperature of 35 ° C. or higher, and on the attrition resistance in the production apparatus during the large-scale production of the titanium catalyst component. .

The present invention aims to provide a titanium catalyst component for producing an olefin polymer capable of producing an olefin polymer having extremely high transparency and extremely high crystallinity, which is extremely low in void generation with extremely high productivity, and a method for producing the same. It is what

[Means for Solving the Problems]

 The present invention has the following configurations.

(1) Liquefied magnesium compound and halogen or halogen compound, electron donor and general formula Ti (OR ¹⁰ ).
_4-u X _u (wherein R ¹⁰ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u represents 0 <u ≦
A titanium compound (T ₁ ) represented by any number of 4)
In the presence of an organoaluminum compound, the solid product (I) obtained by contacting
Alternatively, a final solid product (III) obtained by polymerizing trialkylsilylstyrene to obtain a solid product (II) and reacting the solid product (II) with a titanium halide compound (T ₂ ). An olefin containing 0.01% to 99% by weight of a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer and containing titanium, magnesium, halogen, and an electron donor as essential components. Titanium catalyst component for polymer production.

(2) Liquefied magnesium compound and halogen or halogen compound, electron donor and general formula Ti (OR ¹⁰ ).
_4-u X _u (wherein R ¹⁰ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u represents 0 <u ≦
A titanium compound (T ₁ ) represented by any number of 4)
In the presence of an organoaluminum compound, the solid product (I) obtained by contacting
Alternatively, a final solid product (III) obtained by polymerizing trialkylsilylstyrene to obtain a solid product (II) and reacting the solid product (II) with a titanium halide compound (T ₂ ). And containing 0.01% to 99% by weight of crystalline dialkyldiallylsilane polymer and / or crystalline trialkylsilylstyrene polymer, and titanium, magnesium, halogen, and electron donor as essential components. A method for producing a titanium catalyst component for producing an olefin polymer, the method comprising:

(3) As the organoaluminum compound, the general formula is AlR ¹ _m R
² _{m ′} X _{3- (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and m, m ′ Is 0
<M + m ′ ≦ 3 represents an arbitrary number. The manufacturing method of the said 2nd item which uses the organoaluminum compound represented by these.

The titanium catalyst component for olefin polymerization of the present invention contains a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer (hereinafter sometimes referred to as a specific silicon-containing polymer), and A titanium catalyst component for olefin polymerization, which contains titanium, magnesium, halogen, and an electron donor as essential components,
The manufacturing method will be described.

The term “liquefaction” of the magnesium compound as used in the present invention means that the magnesium compound itself becomes a liquid, the case where the magnesium compound itself is soluble in a solvent to form a solution, and the case where the magnesium compound reacts with other compounds. Alternatively, it also includes the case where a solution is formed by being solubilized in a solvent as a result of forming a complex. Further, the solution may be in the state of containing a colloidal or semi-dissolved substance in addition to the case of being completely dissolved.

The magnesium compound to be liquefied may be any as long as it can be in the above-mentioned "liquefied" state, for example, magnesium dihalide, alkoxy magnesium halide, aryloxy magnesium halide, dialkoxy magnesium, diaryloxy. In addition to magnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate, dialkyl magnesium, alkyl magnesium halide, and the like, metal magnesium can be used. Further, these magnesium compound or metallic magnesium may be a reaction product with an electron donor, a silicon compound or an aluminum compound.

As a method of liquefying the magnesium compound, known means are used. For example, a magnesium compound is an alcohol,
Liquefaction with aldehydes, amines or carboxylic acids (JP-A-56-811), liquefaction with orthotitanate (JP-A-54-40,293), liquefaction with phosphorus compounds In addition to the method (Japanese Patent Laid-Open No. 58-19,307, etc.) and the like, a method in which these are combined is also included. In addition, it is not possible to apply the above method, for the organomagnesium compound having a C-Mg bond, since it is soluble in ether, dioxane, pyridine, etc., it is used as a solution of these, or by reacting with an organometallic compound, The general formula is M _p Mg _q R ³ _r R ⁴ _s (M is aluminum, zinc, boron, or beryllium atom, R ³ and R ⁴ are hydrocarbon residues,
If p, q, r, s> 0, and v are M valences, r + s =
There is a relationship of vP + 2q. ) Can be formed into a complex compound (see JP-A-50-139,885) and dissolved in a hydrocarbon solvent to be liquefied.

Furthermore, in the case of using metallic magnesium, a method of liquefying with an alcohol and an orthotitanate ester (Japanese Patent Laid-Open No. 5051/587, etc.) or reacting with an alkyl halide in ether to form a so-called Grignard reagent It can be liquefied by a method.

In the method of liquefying a magnesium compound as described above, for example, the case of dissolving magnesium chloride in a hydrocarbon solvent (D ₁ ) using a titanate ester and an alcohol will be described. Using 0.1 mol to 2 mol of titanic acid ester, 0.1 mol to 5 mol of alcohol, and 0.1 to 5 l of solvent (D ₁ ),
The components are mixed in any order of addition, and the suspension is heated with stirring at 40 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours.

Examples of the titanic acid ester include orthotitanic acid ester represented by Ti (OR ⁵ ) ₄ and R ⁶ O-Ti (OR ⁷ ) (O
Examples thereof include polytitanate represented by R ⁸ ) _t OR ⁹ . Here, R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ have 1 to 1 carbon atoms.
It is an alkyl group having 20 or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 2 to 20.

Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, orthotitanate i
Ortho such as propyl, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate. Titanate, polymethyl titanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, polytitanic acid n
-Polytitanate esters such as octyl, phenyl polytitanate and cyclohexyl polytitanate can be used. The amount of polytitanate ester used may be equivalent to orthotitanate ester in terms of orthotitanate ester units.

Aliphatic saturated and unsaturated alcohols can be used as alcohols. Specifically, methanol, ethanol, n-propanol, i-propanol, n-
In addition to monohydric alcohols such as butanol, n-amyl alcohol, i-amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol and allyl alcohol, polyhydric alcohols such as ethylene glycol, trimethylene glycol and glycerin. Can be used. Of these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferable.

Examples of the inert hydrocarbon solvent (D ₁ ) include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2- Mention may be made of halogenated hydrocarbons such as dichloroethane, 1,1,2-trichloroethane, chlorobenzene and 0-dichlorobenzene. Of these, aliphatic hydrocarbons are preferable.

The solid product (I) is obtained by contacting the liquefied magnesium compound with the extruding agent (X ₁ ), halogen compound (X ₂ ), electron donor (B ₁ ) and titanium compound (T ₁ ). .
Examples of the depositing agent (X ₁ ) include halogenating agents such as halogen, halogenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing titanium compounds, halogen-containing zirconium compounds and halogen-containing vanadium compounds.

When the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, such as alcohol or polysiloxane having a Si—H bond, can be used. The amount of these depositing agents (X ₁ ) used is 0.1 mol to 50 mol per 1 mol of the magnesium compound.

Further, examples of the halogen compound (X ₂ ) include halogen and compounds containing halogen, and the same halogenating agents as the examples of the precipitating agent can be used. When used, it does not necessarily require a new use of the halogen compound (X ₂ ). The halogen compound (X ₂ ) is used in an amount of 0.1 mol to 50 mol per mol of the magnesium compound.

As the electron donor (B ₁ ), alcohol, phenol,
Oxygen-containing electron donors such as ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates, phosphines, phosphites. A phosphorus-containing electron donor such as phosphinite can be used.

Specifically, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenol, Cresol, xylenol, phenols such as ethylphenol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ketones such as benzophenone, acetaldehyde, propionaldehyde, aldehydes such as benzaldehyde, formic acid, acetic acid,
Carboxylic acids such as propionic acid, butyric acid and valeric acid, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, octyl acetate, phenyl acetate, propionic acid Aliphatic carboxylic acid esters such as ethyl, methyl benzoate,
Aromatic monocarboxylic acid esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, phenyl anisate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n phthalate -Propyl, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate , Di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate,
Aromatic polyvalent carboxylic acid esters such as dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, di-i-butyl naphthalene dicarboxylate, methyl ether, ethyl ether, isopropyl Ethers such as ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid amide, benzoic acid amide, toluic acid amide and other acid amides, acetic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, tetrahydroanhydride Acid anhydrides such as phthalic acid, amines such as ethylamine, tributylamine, aniline, pyridine, picoline, tetramethylethylenediamine, nitriles such as acetonitrile and benzonitrile, ethylphosphine , Phosphines such as triethylphosphine, tri-n-butylphosphine, and triphenylphosphine; phosphites such as dimethylphosphite, triethylphosphite and triphenylphosphite; phosphinites such as ethyldiethylphosphinite and ethylbutylphosphinite. And alkoxysilanes such as tetraethoxysilane and tetrabutoxysilane are used, preferably aromatic monocarboxylic acid ester acid, aromatic polyvalent carboxylic acid esters, alkoxysilanes, and particularly preferably aromatic polyvalent acid. Carboxylic acid esters are used.

One or more kinds of these electron donors (B ₁ ) are used, and the amount thereof is 0.01 mol to 1 mol of the magnesium compound.
It is 5 mol.

Titanium compound (T ₁ ) required for preparation of solid product (I)
Is the general formula Ti (OR ¹⁰ ) _4-u X _u (wherein R ¹⁰ is an alkyl group,
A cycloalkyl group or an aryl group, X represents halogen, and u is an arbitrary number satisfying 0 <u ≦ 4. The titanium halide compound represented by the formula (1) or the orthotitanate ester or polytitanate ester mentioned in the liquefaction of the magnesium compound is used.

Specific examples of the titanium halide compound, titanium tetrachloride, titanium tetrabromide, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, Butoxy titanium tribromide, dimethoxy titanium dichloride,
Diethoxy titanium dichloride, dipropoxy titanium dichloride,
Dibutoxy titanium dichloride, diphenoxy titanium dichloride,
Examples thereof include diethoxytitanium dibromide, dibutoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, and triphenoxytitanium chloride.

Examples of the orthotitanate and polytitanate include the same ones as described above. One or more kinds of these titanium compounds (T ₁ ) are used. When a titanium halide compound is used as the titanium compound (T ₁ ), since it has halogen, the depositing agent (X ₁ ) and the halogen compound ( The use of X ₂ ) is optional.

Further, even when a titanate ester is used in the liquefaction of the magnesium compound, the new use of the titanium compound (T ₁ ) is optional. The amount of the titanium compound (T ₁ ) used is 0.1 mol to 100 mol per 1 mol of the magnesium compound.

Liquefied magnesium compound, precipitation agent (X ₁ ),
The halogen compound (X ₂ ), the electron donor (B ₁ ) and the titanium compound (T ₁ ) are contacted with stirring to obtain a solid product (I). At the time of contact, an inert hydrocarbon solvent (D ₂ ) may be used, or each component may be diluted in advance and used. Examples of the inert hydrocarbon solvent (D ₂ ) used include the same ones as described above for (D ₁ ). The amount used is 0 to 5,000 ml per mol of the magnesium compound.

There are various contact methods, for example,
(X ₁ ) is added to a liquefied magnesium compound to precipitate a solid, and (X ₂ ), (B ₁ ), and (T ₁ ) are brought into contact with the solid in any order. A method in which (X ₁ ) is added to a solution in which a liquefied magnesium compound and (B ₁ ) are brought into contact with each other to precipitate a solid, and (X ₂ ) and (T ₁ ) are brought into contact with the solid in any order. After contacting the liquefied magnesium compound with (T ₁ ), (X ₁ ) is added, and then (B ₁ ) and (X ₂ ) are contacted in any order.

The amount of each component used is within the above range, but these components may be used at one time or may be used in several stages. Also, as already mentioned, if one component has an atom or group that also characterizes the other component, a new use of the other component is not necessary. For example, when a titanate ester is used for liquefying a magnesium compound (T ₁ ), when a halogen-containing titanium compound is used as a depositing agent (X ₁ ), (X ₂ ) and (T ₁ )
However, when a halogenating agent is used as the precipitating agent (X ₁ ), (X ₂ ) is an optional component to be used.

The contact temperature of each component is −40 ° C. to + 180 ° C., preferably −2
0 ℃ to + 150 ℃, contact time is from atmospheric pressure to 10 ℃
It is 5 minutes to 8 hours, preferably 10 minutes to 6 hours in each step in kg / cm ² G.

A solid product (I) is obtained in the above catalytic reaction.
The solid product (I) may be subsequently reacted in the next step, but it is preferably washed with the above-mentioned inert hydrocarbon solvent.

Next, the solid product (I) obtained by the above method is treated with a dialkyldiallylsilane and / or a trialkylsilylstyrene (hereinafter referred to as a specific silicon-containing monomer) in the presence of the organoaluminum compound (AL ₁ ). Sometimes.)
Polymerization is carried out to obtain a solid product (II).

The polymerization treatment with the specific silicon-containing monomer is carried out by adding 100 g of the solid product (I) to 100 ml of an inert hydrocarbon solvent (D ₃ ).
5,000 ml, organoaluminum compound (AL ₁ ) 0.5 g to 5,000 g
0.01 to 100 kg of a specific silicon-containing monomer at a reaction temperature of 0 to 90 ° C. for 1 minute to 10 hours and a reaction stress of atmospheric pressure to 10 kg / cm ² G. Solid product (II
I), that is, the polymerization is performed so that the content of the specific silicon-containing polymer in the titanium catalyst component of the present invention is 0.01% by weight to 99% by weight. When the content of the specific silicon-containing polymer is less than 0.01% by weight, the effect of improving transparency and crystallinity of the olefin polymer produced by using the titanium catalyst component obtained is insufficient, and also 99% by weight. When it exceeds, the improvement effect is not remarkable and it is economically disadvantageous.

Further, in the polymerization treatment stage, electron donation represented by carboxylic acid esters such as ethyl benzoate, methyl toluate and ethyl anisate, and silane compounds such as phenyltriethoxysilane, diphenyldimethoxysilane and methyltriethoxysilane. It is also possible for the body (B ₂ ) to coexist. Their use amount is 0 to 5,000 g per 100 g of the solid product (I).

Organoaluminum compound used for polymerization (AL ₁ )
The general formula ^{_{A1R 1 m R 2 m 'X}} 3- (m + m') ( wherein R ^1, R ²
Represents a hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group or an alkoxy group, and X represents a halogen,
Further, m and m'represent an arbitrary number of 0 <m + m'≤3. ), And specific examples thereof include trimethylaluminum, triethylaluminum, and tri-n.
-Propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, trii-hexylaluminum, tri2-
Trialkylaluminums such as methylpentylaluminum, tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, dii
-Dialkyl aluminum monohalides such as butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide and diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalides, ethyl aluminum dichloride, i-butyl aluminum dichloride, and other monoalkyl aluminum dihalides, and the like. In addition, alkoxyalkyl aluminums such as monoethoxy diethyl aluminum and diethoxy monoethyl aluminum should be used. You can also Two or more kinds of these organoaluminum compounds may be mixed and used.

As the solvent (D ₃ ), the same inert hydrocarbon solvents as those described above for (D ₁ ) and (D ₂ ) are shown.

The dialkyldiallylsilane and / or trialkylsilylstyrene used in the polymerization treatment has the general formula (CH
₂ = CH-CH ₂ ) ₂ SiR ¹¹ R ¹² or (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.)
Is a specific monomer containing silicon. Specific examples thereof include dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane, p-trimethylsilylstyrene, m-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene and p-ethyldimethylsilylstyrene. .

As described above, the solid product (II) is obtained by performing the polymerization treatment with the specific silicon-containing monomer and washing with the above-mentioned inert hydrocarbon solvent.

Then, the solid product (II) is reacted with a titanium halide compound (T ₂ ) to obtain a titanium catalyst component containing a specific silicon-containing polymer. As the titanium halide compound (T ₂ ), the general formula Ti given as an example of the titanium compound (T ₁ ) necessary for preparing the solid product (I) described above is used.
(OR ¹⁰ ) _4-u X _u (In the formula, R ¹⁰ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u
Is an arbitrary number of 0 <u ≦ 4. The titanium halide compound represented by the formula (1) is used, and similar examples can be mentioned, but titanium tetrachloride is most preferable.

The reaction of the solid product (II) with a halogenated titanium compound and (T _2), relative to the magnesium compound 1 mol in the solid product (II), using a titanium halide compound (T ₂₎ 1 mole or more The reaction temperature is 20 ° C. to 200 ° C. and the reaction pressure is atmospheric pressure to 10 kg / cm ² G for 5 minutes to 6 hours, preferably 10 minutes to 5 hours. It is also possible to carry out the reaction in the presence of an inert hydrocarbon solvent (D ₄ ) or an electron donor (B ₃ ), and specifically, the above-mentioned (D ₁ ) to (D ₃ )
The same inert solvent and electron donor as those used in (B ₁ ) are used.

The amount of these used is 0 to 5,000 ml for (D ₄ ) with respect to 100 g of the solid product (II), and 0 to 2 mol for (B ₃ ) with respect to 1 mol of the magnesium compound in the solid product (II). The range of is desirable. After reacting the solid product (II) with the titanium halide compound (T ₂ ) and, if necessary, an electron donor, the solid is separated by filtration or decantation and washed with an inert hydrocarbon solvent. The reaction product or by-product is removed to obtain the fixed product (III).

Thus, 0.01% by weight of the particular silicon-containing polymer of the present invention.
A solid product (III) containing from about 99% by weight and containing titanium, magnesium, halogen, and an electron donor as essential components, that is, a titanium catalyst component for producing an olefin polymer of the present invention is obtained.

The titanium catalyst component containing the specific silicon-containing polymer of the present invention obtained as described above can be used in the same manner as the known titanium catalyst component for producing an olefin polymer such as polypropylene.

The specific titanium-containing polymer-containing titanium catalyst component includes an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ )
It is used in olefin polymerization as a catalyst that is pre-activated by polymerizing a small amount of olefin in combination with a catalyst.

Organoaluminum compounds used for olefin polymerization (AL
_{As 2} ), the same organoaluminum compound as (AL ₁ ) used for obtaining the titanium catalyst component of the present invention described above can be used. The electron donor (B ₄ ) is preferably an organic acid ester, an organosilicon compound having a Si-OC bond such as an alkoxysilane compound or an aryloxysilane compound, an ether, a ketone, an acid anhydride, or an amine. . Specifically, other than those exemplified as the electron donors (B ₁ ) to (B ₃ ) used in producing the titanium catalyst component described above, 2,2,6,6-tetramethylpiperidine, 2,2,
Amines with large steric hindrance such as 5,5-tetramethylpyrrolidine, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, and ethyltriethylsilane. Ethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii-propoxysilane, vinyl An organosilicon compound having a Si—OC bond such as triacetoxysilane may be mentioned.

The amount of each catalyst component used is the same as in the case of ordinary olefin polymerization, but specifically, to 1 g of the titanium catalyst component, an organoaluminum compound (AL ₂ ) 0.005 to 500 g, an electron donor (B ₄ ) 0.01 It is about g ~ 200g.

As the olefin used for pre-activation, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1, 4-olefins
Branched chain monoolefins such as methyl-pentene-1, 2-methyl-pentene-1 and the like.

These olefins may be the same as or different from the olefin to be polymerized, or two or more olefins may be mixed and used.

The olefin polymerization method using the above catalyst is not limited, and in addition to liquid phase polymerization such as slurry polymerization and bulk polymerization,
It can also be suitably carried out by gas phase polymerization.

For slurry polymerization or bulk polymerization, titanium catalyst component and organoaluminum compound (AL ₂ ) and electron donor (B ₄ )
Although a sufficient effect can be obtained with a combination of the above catalysts, in the case of gas phase polymerization, a catalyst obtained by reacting an olefin with preactivation is preferable. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, it is the same as the latter catalyst because the olefin reaction has already been carried out during gas phase polymerization. And an excellent effect is obtained.

The pre-activation can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, benzene and toluene, and even in the case of liquefied olefins such as liquefied propylene and liquefied butene-1, ethylene,
It can be carried out also in propylene, and hydrogen may be allowed to coexist during the preliminary activation.

Polymer particles obtained by slurry polymerization, bulk polymerization or gas phase polymerization in advance may be allowed to coexist during the preliminary activation. The polymer may be the same as or different from the olefin polymer to be polymerized. The polymer particles to be coexisted are 0 to 5,000 with respect to 1 g of the titanium catalyst component.
It is in the range of 0g.

The solvent or olefin used in the pre-activation can be removed during the pre-activation or after completion of the pre-activation by distillation under reduced pressure or by filtration, etc. Solvents can also be added for suspension in an amount that does not exceed.

As described above, the catalyst comprising the titanium catalyst component of the present invention, the organoaluminum compound (AL ₂ ) and the electron donor (B ₄ ) combined with each other, or the catalyst pre-activated with olefin is a polymer of olefin. Used in manufacturing.
As a polymerization method for polymerizing an olefin, as described above, n-pentane, n-hexane, n-heptane,
Slurry polymerization performed in a hydrocarbon solvent such as n-octane, benzene, or toluene, bulk polymerization performed in a liquefied olefin monomer such as liquefied propylene or liquefied butene-1, gas phase in which an olefin such as ethylene or propylene is polymerized in a gas phase There is a method of polymerization or a stepwise combination of two or more of the above. In either case, the polymerization temperature is room temperature (20 ℃) to 200 ℃, and the polymerization pressure is normal pressure (0kg / cm ²
G) to 50 kg / cm ² G, and usually 5 minutes to 20 hours.

At the time of polymerization, addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as in the conventional polymerization method.

The olefins used for the polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 4-methylpentene-1,
Branched-chain monoolefins such as 2-methyl-pentene-1 and diolefins such as butadiene, isoprene, and chloroprene, and not only homopolymerization of each of these, but also mutually combining with other olefins. It is also possible to carry out copolymerization by combining, for example, propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or by combining three components such as propylene, ethylene and butene-1. Block copolymerization can be carried out by changing the kind of olefin fed in the polymerization.

[Action]

The olefin polymer obtained by using the titanium catalyst component of the present invention contains a highly stereoregular specific silicon-containing polymer in an extremely dispersed state. By exhibiting a nucleating action,
As a result of reducing the spherulite size of the olefin polymer and promoting crystallization, the transparency and crystallinity of the entire olefin polymer are also increased.

Further, since the specific silicon-containing polymer introduced into the olefin polymer by using the titanium catalyst component of the present invention is the stereoregular high molecular weight polymer as described above, it does not bleed on the surface. .

[Effect of the Invention] The main effect of the present invention is that when the titanium catalyst component of the present invention is used as a transition metal compound catalyst component for producing an olefin polymer in the polymerization of olefins, voids are generated with remarkably high productivity. It is possible to produce an olefin polymer having extremely low transparency and extremely high crystallinity.

The effects of the present invention will be described more specifically.

The first effect of the present invention, when used in olefin polymerization,
Both the transparency and crystallinity of the obtained olefin polymer are improved, and the number of generated voids is extremely small.

As is apparent from the examples shown below, the internal haze of the press film of the olefin polymer obtained using the titanium catalyst component of the present invention does not contain a specific silicon-containing polymer, and is obtained using the titanium catalyst component. Compared with the obtained olefin polymer, it is about 1/8 to 1/4 and has extremely high transparency.

Also, the crystallization temperature is increased by about 7 ° C to 12 ° C as compared with the case where the specific silicon-containing polymer is not contained, and the crystallinity is remarkably improved and the flexural modulus is also remarkably increased. 1-9, Comparative Examples 1, 5-10).

Furthermore, it is clear that the number of voids generated is significantly smaller than that of an olefin polymer in which a polymer of styrenes or silanes is introduced by a method other than the present invention (see Examples 1 to 9 and Comparative Examples 2 and 3). ).

The second effect of the present invention is an extremely high polymerization activity,
That is, an olefin polymer having a good particle shape and high stereoregularity can be obtained. Therefore, the catalyst removal step and the atactic polymer removal step can be omitted, and the olefin polymer can be produced by a continuous polymerization method for a long period by a simpler process such as a gas phase polymerization method. It is extremely advantageous.

The third effect of the present invention is that the titanium catalyst component for producing an olefin polymer of the present invention is excellent in storage stability and thermal stability. It is extremely important industrially to be able to store stably for a long period of time regardless of whether the outside temperature is high or low. In addition,
The preservation can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Further, the fourth effect of the present invention is that the titanium catalyst component for producing an olefin polymer of the present invention has excellent abrasion resistance. The titanium catalyst component is less susceptible to attrition 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 is extremely effective in preventing line blockage troubles in the gas phase polymerization process, and preventing compressor troubles due to mixing of the finely divided olefin polymer into the circulating gas.

[Examples] Hereinafter, the present invention will be described with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

TY: Polymerization activity, polymer yield per 1 gram atom of titanium (unit: kg / gram atom) II: Stereoregularity, boiling n-heptane extraction residual amount (unit: wt%) BD: Bulk specific gravity ( Unit: g / ml) MFR: Melt flow index According to ASTM D-1238 (L). (Unit: g / 10 minutes) Internal haze: The internal haze excluding the effect of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg / cm ² G
Under the conditions, the olefin polymer powder was formed into a film having a thickness of 150 μ, liquid paraffin was applied to both surfaces of the film, and then the haze was measured according to JIS K 7105. (unit:
%) Crystallization temperature: measured by a temperature decrease measurement of 10 ° C./min using a differential scanning calorimeter. (Unit: ° C) Flexural modulus: Tetrakis [methylene-3- (3 ', 5'-di-t] based on 100 parts by weight of olefin polymer powder
-Butyl-4'-hydroxyphenyl) propionate] methane 0.1 part by weight, and calcium stearate
0.1 parts by weight were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, the granulated product is made into a JIS type test piece at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine, and the humidity of the test piece is 50%
After being left for 72 hours in a room at room temperature of 23 ° C., the flexural modulus was measured according to JIS K 7203. (Unit: kgf / cm ² ) Void: The olefin polymer was granulated in the same manner as in the previous section, and the obtained granulated product was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine. A sheet having a thickness of 1 mm was prepared with a cooling roll at ℃. The sheet is heated with hot air at 150 ° C. for 70 seconds and stretched 7 times in the machine and transverse directions using a biaxial stretching machine,
A biaxially stretched film having a thickness of 20 μ was obtained. The film is observed with an optical microscope, the number of voids having a diameter of 10μ or more is measured, and less than 20 per 1 cm ² is ○, 20 to less than 50 is Δ, 50
More than one is indicated by x.

Example 1 (1) Production of titanium catalyst component In a stainless reactor equipped with a stirrer, decane 3 l, anhydrous magnesium chloride 480 g, and n-butyl orthotitanate 1.
7 kg and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated at 130 ° C. for 1 hour with stirring to dissolve them to obtain a uniform solution. The homogeneous solution was heated to 70 ° C., 180 g of diisobutyl phthalate was added with stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid.
Heated to ° C for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (I).

450 g of triethylaluminum and 145 g of diphenyldimethoxysilane whose total amount of the solid product (I) was maintained at 30 ° C.
After suspending in 10 liters of hexane containing hexane, 2.9 kg of dimethyldiallylsilane was added, and the mixture was stirred at the same temperature for 2
Polymerization was performed for a time. After the treatment, the operation of removing the supernatant liquid, adding 6 liters of n-hexane, and removing the supernatant liquid by decantation was repeated 4 times to obtain a polymerized solid product (II).

The total amount of the solid product (II) was mixed with 5 liters of titanium tetrachloride dissolved in 5 liters of 1,2-dichloroethane, subsequently 180 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. The liquid phase was removed by decantation at temperature, 5 l of 1,2-dichloroethane and 5 l of titanium tetrachloride were added again, and the mixture was stirred at 100 ° C for 2 hours, washed with hexane and dried to obtain a solid product (III). The titanium catalyst component of the present invention. The titanium catalyst component had a particle shape close to a sphere, and contained 1.5% by weight of titanium and 50.0% by weight of a crystalline dimethyldiallylsilane polymer.

(2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 30 l with nitrogen gas, 20 l of n-hexane, 1.5 kg of triethylaluminum, 480 g of diphenyldimethoxysilane and titanium obtained with (1) 200 g of catalyst component was added at room temperature. The reactor was kept at 30 ° C., and 180 Nl of ethylene was fed at the same temperature for 2 hours for reaction (per 1 g of titanium catalyst component,
After reacting 1.0 g of ethylene), unreacted ethylene was removed to obtain a preactivated catalyst.

(3) Polymerization of olefin After 20 kg of polypropylene powder of MFR 2.0 was charged into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer having an internal volume of 80 liter and replaced with nitrogen, the pre-activated catalyst slurry (other than titanium catalyst component) was added. (Containing triethylaluminum and diphenyldimethoxysilane) were continuously supplied at 0.285 mg atom / hr in terms of titanium atom. The concentration in the gas phase is 0.1
Hydrogen was supplied so as to maintain 5% by volume and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G, and vapor phase polymerization of propylene was continuously carried out at 70 ° C. for 120 hours. During the polymerization period, the polymer was continuously withdrawn from the polymerization vessel at 10 kg / hr so that the retained level of the polymer in the polymerization vessel was 60% by volume. The polymer extracted was subsequently obtained as a product powder after being contact-treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 15 minutes.

(4) Thermal stability test The titanium catalyst component obtained in the same manner as in (1) above was tested at 40 ° C for 4 hours.
After storage for a month, propylene was polymerized in the same manner as (2) and (3).

(5) Attrition resistance test After connecting a circulation pipe equipped with a circulation pump to the reactor used in (2), 20 l of n-hexane was added under a nitrogen atmosphere.
And 200 g of titanium catalyst component obtained in the same manner as (1) above
I put it in. Then, the circulation pump was operated, and the suspension in the reactor was circulated for 4 hours under the conditions of a flow rate of 10 l / min and a temperature of 25 ° C. using a circulation line, and then the same procedure as (2) and (3) The propylene was polymerized.

Comparative Example 1 (1) A titanium catalyst component was prepared in the same manner as in Example 1 (1) except that the solid product (I) was converted to the solid product (II) equivalent without being polymerized with dimethyldiallylsilane. Got

(2) A preactivated catalyst was prepared in the same manner as in Example 1 (2) except that 100 g of the titanium catalyst component obtained in (1) above was used as the titanium catalyst component.

(3) Polymerization of propylene was carried out in the same manner as in Example 1 (3) except that the preliminary activation catalyst obtained in the above (2) was used as the preliminary activation catalyst.

(4) Propylene polymerization was carried out in the same manner as in (4) of Example 1 except that the titanium catalyst component obtained in the same manner as in (1) above was used as the titanium catalyst component.

(5) Polymerization of propylene was carried out in the same manner except that the titanium catalyst component obtained in the same manner as in the above (1) was used as the titanium catalyst component in (5) of Example 1.

Comparative Example 2 (1) A titanium catalyst component was obtained in the same manner as in (1) of Comparative Example 1.

(2) 20 l of n-heptane, 100 g of the titanium catalyst component obtained in (1) above, 400 g of diethylaluminum monochloride 400 g, and 120 g of diphenyldimethoxysilane were added to the reactor used in (2) of Example 1, and then allyl was added. Trimethylsilane
250 g was added and reacted at 40 ° C for 2 hours (titanium catalyst component
Allyltrimethylsilane 1.0 g reaction per 1 g). Then n
-After washing with heptane, filtration gave a solid. Further, 20-liter of n-heptane, 400 g of diethylaluminum monochloride,
After adding 55 g of diphenyldimethoxysilane, 280 g of propylene was supplied and reacted at 30 ° C. for 1 hour (1.8 g of propylene reacted per 1 g of titanium catalyst component).

(3) In place of the preactivated catalyst slurry in (3) of Example 1, the catalyst slurry obtained in (2) above was further added with triethylaluminum at 1.7 g / hr and diphenyldimethoxysilane at 0.3 g / hr, Polymerization of propylene was carried out in the same manner except that they were supplied from different supply ports.The produced bulk polymer clogged the powder extraction pipe, so the production must be stopped 12 hours after the start of polymerization. I had to do it.

Comparative Example 3 (1) Before adding diisobutyl phthalate to a uniform solution of anhydrous magnesium chloride, n-butyl orthotitanate, 2-ethyl-1-hexanol and decane in (1) of Comparative Example 1, a comparison was made separately. 100 g of titanium catalyst component obtained in the same manner as in (1) of Example 1 and triethylaluminum 35
g, and 4.3 kg pt added into 100 l of n-hexane using 7.5 g of diphenyldimethoxysilane as a catalyst.
-Butylstyrene was polymerized at 60 ° C for 2 hours, washed with methanol, and dried to obtain 550 g of 3 kg of pt-butylstyrene polymer obtained by pulverizing in a vibration mill for 5 hours, and then homogenizing the mixture. A titanium catalyst component was obtained in the same manner as in (1) of Comparative Example 1 except that the titanium catalyst component was suspended in the solution.

(2) A preactivated catalyst was obtained in the same manner as in (2) of Example 1 except that the titanium catalyst component obtained in (1) above was used as the titanium catalyst component.

(3) In (3) of Example 1, the pre-activated catalyst obtained in (2) above was used as the pre-activated catalyst at a total pressure of 23 kg / cm ^2.
Polymerization of propylene was carried out in the same manner except that G was supplied so as to be maintained.

Comparative Example 4 and Examples 2 and 3 By changing the amount of 2,4-dimethylstyrene used in the polymerization treatment in Example 1 (1), the content of 2,4-dimethylstyrene polymer was 0.001% by weight, respectively. , 4.8% by weight,
33.3 wt% titanium catalyst component was obtained. After that, propylene was polymerized in the same manner as in (2) and (3) of Example 1.

Example 4 When 1.7 kg of aluminum trichloride (anhydrous) and 0.6 kg of magnesium hydroxide were reacted with each other while being pulverized at 250 ° C. for 3 hours in a vibration mill, the reaction occurred while generating hydrogen chloride gas. After the heating was completed, it was cooled in a nitrogen stream to obtain a magnesium-containing solid.

In a stainless steel reactor equipped with a stirrer, decane 6 l,
1.0 kg of magnesium-containing solid, 3.4 kg of n-butyl orthotitanate, and 3.9 kg of 2-ethyl-1-hexanol were mixed and heated to 130 ° C. for 2 hours with stirring to dissolve to obtain a uniform solution. The solution was heated to 70 ° C, 0.2 kg of ethyl p-toluate was added and reacted for 1 hour, then 0.4 kg of diisobutyl phthalate was added and further reacted for 1 hour, and 10 kg of silicon tetrachloride was added dropwise over 2 hours and 30 minutes while stirring. Then, a solid was precipitated and further stirred at 70 ° C. for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (I).

The total amount of the solid product (I) was suspended in 10 l of hexane containing 450 g of triethylaluminum and 75 g of methyl p-toluate kept at 25 ° C., and then dimethyldiallylsilane.
2.8 kg was added, and a polymerization treatment was carried out at the same temperature for 2 hours while stirring. After the treatment, remove the supernatant and n-hexane 6l
Was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (II) subjected to polymerization treatment.

The total amount of the solid product (II) was diluted with 10 liters of 1,2-dichloroethane together with 10 liters of titanium tetrachloride and diisobutyl phthalate.
After adding 0.4 kg and reacting at 100 ° C for 2 hours with stirring, the liquid phase part was removed by decantation at the same temperature,
10l of 1,2-dichloroethane and 10l of titanium tetrachloride were added again, and the mixture was reacted at 100 ° C for 2 hours with stirring, filtered by hot filtration to collect a solid portion, washed with purified hexane, and dried to obtain a solid product. (III) was obtained as the final titanium catalyst component. The titanium content of the titanium catalyst component was 1.84% by weight, and the crystalline dimethyldiallylsilane polymer content was 45.9% by weight.

Then, 500 g of phenyltriethoxysilane instead of diphenyldimethoxysilane in (2) of Example 1,
Further, a preactivated catalyst was obtained in the same manner as above except that the above solid product (III) was used as the titanium catalyst component, and then propylene gas phase polymerization was carried out in the same manner as in (3) of Example 1.

Comparative Example 5 A titanium catalyst component was obtained in the same manner as in Example 4 except that the solid product (I) was converted to the solid product (II) equivalent without polymerizing with dimethyldiallylsilane. Polymerization was carried out.

Example 5 8 l of n-heptane in a stainless steel reactor equipped with a stirrer,
1.0 kg of anhydrous magnesium chloride and 7.4 kg of n-butyl orthotitanate were mixed, heated to 90 ° C. with stirring, and heated for 2 hours to dissolve to obtain a uniform solution. Then the homogeneous solution
After cooling to 40 ° C., 1,500 ml of methyl hydrogen polysiloxane was added dropwise to deposit a solid. This was washed with n-heptane to obtain an off-white solid. 500 g of the solid and 7 l of n-heptane were placed in a stainless steel reactor equipped with a stirrer. Then add 100 g of diisobutyl phthalate and after 1 hour at 30 ° C,
A mixed solution of 11.3 kg of silicon tetrachloride and 500 g of titanium tetrachloride was added dropwise over 1 hour. Then at 30 ℃ for 30 minutes, then 90 ℃ 1
Reacted for hours. The solid was separated from the solution and washed with n-heptane to give a solid product (I).

200 g of triethylaluminum in which 2.5 mol of the solid product (I) in terms of magnesium atom is kept at 30 ° C.
And 5 g of n-heptane containing 60 g of diphenyldimethoxysilane and p-trimethylsilylstyrene
550 g was added, and polymerization was performed at the same temperature for 2 hours while stirring. After the treatment, the solid is separated from the solution, washed with n-heptane, and subjected to a polymerization treatment to obtain a solid product (II).
Got

The whole solid product (II) was mixed with 12 liters of n-heptane solution containing 6 liters of titanium tetrachloride, followed by diheptyl phthalate 100.
After adding g and making it react at 50 degreeC for 2 hours, it wash | cleaned by n-heptane, 150 ml of titanium tetrachloride was further added, and it wash | cleaned at 90 degreeC, and the solid product (III) was obtained. The titanium content of the solid product (III) was 1.76% by weight, and the crystalline p-trimethylsilylstyrene polymer content was 41.2% by weight.

Subsequently, in (2) of Example 1, 150 g of t-butyltriethoxysilane was used instead of diphenyldimethoxysilane.
And the solid product (II
I) A preactivated catalyst was obtained in the same manner except that the whole amount was used, and then propylene vapor-phase polymerization was carried out in the same manner as in (3) of Example 1.

Comparative Example 6 A titanium catalyst component was obtained in the same manner as in Example 5 except that the solid product (I) was converted to the solid product (II) equivalent without polymerizing with p-trimethylsilylstyrene. Was vapor-phase polymerized.

Example 6 n-decane was added in a stainless steel reactor equipped with a stirrer.
2.5 l, anhydrous magnesium chloride 480 g and 2-ethyl-1
-Hexanol (1.95 kg) is heated at 130 ° C for 2 hours to dissolve it into a uniform solution, and then 111 g of phthalic anhydride is added to this solution.
Was added, and the mixture was further stirred and mixed at 130 ° C. to dissolve phthalic anhydride into the homogeneous solution. The homogeneous solution thus obtained was cooled to room temperature, and then the entire amount was added dropwise to 10 l of titanium tetrachloride kept at -20 ° C over 1 hour. After dropping
The temperature of this mixture was raised to 110 ° C over 4 hours,
When the temperature reached, the solid reacted with stirring at the same temperature for 2 hours was separated from the solution and washed with hexane to obtain a solid product (I).

450 g of triethylaluminum and 145 g of diphenyldimethoxysilane in which the total amount of the solid product (I) was kept at 40 ° C.
After suspending it in 10 l of n-decane containing, 2.9 kg of dimethyldiallylsilane was added, and a polymerization treatment was carried out at the same temperature for 2 hours while stirring. After the treatment, the solid was separated from the solution, washed with hexane and subjected to a polymerization treatment to give a solid product (I
I) got. The total amount of the solid product (II) was mixed with 10 l of titanium tetrachloride, 350 g of diisobutyl phthalate was subsequently added, and the mixture was reacted at 110 ° C. for 2 hours while stirring, and then decanted at the same temperature to form a liquid phase. After removing the parts, 1,000 ml of titanium tetrachloride was added again, and the mixture was heated at 110 ° C. for 2 hours for heating reaction.

After completion of the reaction, the liquid phase was removed by decantation at the same temperature, the solid was washed with n-decane and n-hexane at 80 ° C, and dried to obtain a solid product (III).
This was the final titanium catalyst component. The titanium catalyst component comprised 1.54 wt% titanium and 48.7 wt% crystalline dimethyldiallylsilane polymer. Subsequently, the internal volume is 200 l
N-hexane was added to the above titanium catalyst component in a polymerization vessel equipped with a stirrer equipped with a two-stage turbine blade to prepare a 4.0 wt% n-hexane suspension, and the suspension was converted into titanium atoms in an amount of 0.
385 mg atom / hr, 8.5 g triethylaluminum
/ hr and diphenyldimethoxysilane at 3.0 g / hr were continuously supplied from the same pipe, and n-hexane was continuously supplied at 21 kg / hr from another pipe. Furthermore, the concentration in the gas phase of the polymerization vessel is 0.
Hydrogen was supplied so as to maintain 25% by volume and propylene was supplied so that the total pressure was maintained at 8 kg / cm ² G, and slurry polymerization of propylene was continuously carried out at 70 ° C. for 120 hours. During the polymerization period, the slurry was continuously withdrawn from the polymerization vessel into a flash tank having an internal volume of 50 l so that the retained level of the slurry in the polymerization vessel was 75% by volume. While the pressure was reduced in the flash tank to remove unreacted propylene, methanol was supplied at 1 kg / hr and contact treatment was performed at 70 ° C. Subsequently, the slurry was separated from the solvent by a centrifuge and then dried by a drier to continuously obtain a product powder at 10 kg / hr.

Comparative Example 7 Using the titanium catalyst component obtained in the same manner as in Example 6, except that the solid product (I) was replaced with the solid product (II) without the polymerization treatment with dimethyldiallylsilane. The slurry polymerization of propylene was carried out in the same manner as in Example 6.

Example 7 A solid product (III) obtained in the same manner as in Example 1 (1) except that 580 g of magnesium ethoxide and 2.8 kg of dimethyldiallylsilane were used instead of anhydrous magnesium chloride. Was used as the final titanium catalyst component, and thereafter, vapor phase polymerization of propylene was carried out in the same manner as in (2) and (3) of Example 1.

Comparative Example 8 A titanium catalyst component was obtained in the same manner as in Example 7 except that the solid product (I1) was changed to the solid product (II) equivalent without the polymerization treatment with dimethyldiallylsilane. Polymerization was carried out.

Example 8 In (1) of Example 1, 1.2k of n-butyl polytitanate (pentamer) was used instead of n-butyl orthotitanate.
g, and a titanium catalyst component was obtained in the same manner except that 0.6 kg of p-tolumethylsilylstyrene was used instead of dimethyldiallylsilane. Then, using the titanium catalyst component thus obtained, propylene was polymerized in the same manner as in (2) and (3) of Example 1.

Comparative Example 9 A titanium catalyst component was obtained in the same manner as in Example 8 except that the solid product (I) was replaced with the solid product (II) without the polymerization treatment with p-trimethylsilylstyrene. Was polymerized.

Example 9 In Example 6, except that the amount of dimethyldiallylsilane used in obtaining the titanium catalyst component was 2.4 kg, and ethylene was further supplied so that the concentration in the gas phase was 0.2% by volume during propylene polymerization. Similarly, propylene-ethylene copolymerization was performed.

Comparative Example 10 A titanium catalyst component was obtained in the same manner as in Example 9 except that the solid product (I) was replaced with the solid product (II) without the polymerization treatment with dimethyldiallylsilane. Ethylene copolymerization was performed.

The polymerization conditions and evaluation results of Examples 1 to 9 and Comparative Examples 1 to 10 described above are shown in the table below.

[Brief description of drawings]

FIG. 1 is a flow sheet for explaining the manufacturing process of the present invention.

Claims (3)

[Claims] 1. A liquefied magnesium compound and a halogen or a halogen compound, an electron donor and a general formula Ti (OR
¹⁰ ) _4-u X _u (wherein R ¹⁰ is an alkyl group, a cycloalkyl group,
Or an aryl group, X represents halogen, and u is 0 <
a solid product (I) obtained by contacting a titanium compound (T ₁ ) represented by u ≦ 4) in the presence of an organoaluminum compound with dialkyldiallylsilane and / or trialkylsilylstyrene To obtain a solid product (II), which is a final solid product (III) obtained by reacting the solid product (II) with a titanium halide compound (T ₂ ). Titanium for producing an olefin polymer containing 0.01% by weight to 99% by weight of a dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, and containing titanium, magnesium, halogen and an electron donor as essential components. Catalyst component. 2. A liquefied magnesium compound and a halogen or a halogen compound, an electron donor and a general formula Ti (OR
¹⁰ ) _4-u X _u (wherein R ¹⁰ is an alkyl group, a cycloalkyl group,
Or an aryl group, X represents halogen, and u is 0 <
a solid product (I) obtained by contacting a titanium compound (T ₁ ) represented by u ≦ 4) in the presence of an organoaluminum compound with dialkyldiallylsilane and / or trialkylsilylstyrene To obtain a solid product (II), which is a final solid product (III) obtained by reacting the solid product (II) with a titanium halide compound (T ₂ ). An olefin containing 0.01% by weight to 99% by weight of a dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, and titanium, magnesium, halogen, and an electron donor as essential components. A method for producing a titanium catalyst component for producing a polymer. 3. An organoaluminum compound having the general formula
AlR ¹ _m R ² _{m ′} X _{3 − (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; m,
m ′ represents an arbitrary number of 0 <m + m ′ ≦ 3. The manufacturing method of Claim 2 which uses the organoaluminum compound represented by these.