JPH0784499B2 - Titanium catalyst component for olefin polymerization and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a titanium catalyst component for olefin polymerization and a method for producing the same. More specifically, it relates to a titanium catalyst component for olefin polymerization, which is suitable as a transition metal compound catalyst component for producing a highly crystalline polyolefin having excellent transparency, and a method for producing the same.

[Conventional technology and its problems]

A crystalline polyolefin such as crystalline polypropylene is obtained by polymerizing an olefin with a so-called Ziegler-Natta catalyst, which is composed of a transition metal compound of Group IV to VI and an organic compound of a metal of Group I to III of the periodic table. Is well known, and a method for obtaining a polyolefin having high polymerization activity and high stereoregularity has been pursued.
Among them, a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor is used as a substance which exhibits remarkably high polymerization activity while maintaining high stereoregularity. In recent years, vigorous studies have been made on a method for producing a polyolefin by polymerizing an olefin with a catalyst in which these are combined. (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-62-10.
4,810, JP-A-62-104,811 and JP-A-62-10
In Japanese Patent No. 4,812 and Japanese Patent Laid-Open No. 62-104,813, a method for obtaining a polyolefin having a high stereoregularity and a good particle shape with a remarkably high polymerization activity is disclosed.

However, although these improved methods have the advantages as described above, the obtained polyolefin is translucent, which may impair the commercial value in the application field, and improvement in transparency has been desired. .

On the other hand, attempts have been made to improve the transparency of polyolefins, such as aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22740). There is a method of adding a nucleating agent such as polypropylene 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, and, When a benzylidene sorbitol derivative was used, although some improvement in transparency was observed, it had problems such as strong odor during processing and bleeding of additives (embossing).

To improve the above problems when adding the nucleating agent, propylene, α-olefin having 4 to 18 carbon atoms, and 3-
Method of copolymerizing methylbutene-1 (Japanese Patent Publication No.
No. 30), or a method of carrying out polymerization of vinylcyclohexane and propylene in multiple stages (Japanese Patent Laid-Open No. 60-139,710) has been proposed. However, the inventors of the present invention produced polypropylene according to the proposed method. However, not only does the polymerization activity decrease in any of the methods, but a lumpy polymer is produced. Therefore, an industrial long-term continuous polymerization method, in particular, a gas phase polymerization method in which olefin polymerization is carried out in a gas phase. It was a method that could not be adopted in. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

Further, a method of producing a highly crystalline polypropylene by polymerizing a small amount of trialkylvinylsilane such as vinyltrimethylsilane or trialkylallylsilane, and then polymerizing propylene using the same method (JP-A-63) -15,804) is proposed, but the specification of the publication does not show any data on the transparency of the obtained polypropylene, and the same method also reduces the polymerization activity and the formation of a lump polymer. Also, there is a problem that voids are generated in the film.

Further, as a method for improving these multi-stage polymerization techniques, a method of selectively using an organoaluminum compound in multiple stages (JP-A-62-62)
No. 275,110, JP-A-63-37,104) and a method in which a small amount of propylene is polymerized batchwise before the main polymerization of propylene (JP-A-63-37,105) is used to suppress the decrease in polymerization activity and boiling n-. Although proposed for the purpose of suppressing the decrease in the heptane extraction residual rate, the formation of a lump polymer and the generation of a film void cannot be suppressed by any of the improved methods.

The present inventors, when producing a polyolefin with improved transparency, by the technique of performing multi-stage polymerization in the presence of a catalyst system already formed by any of the conventional techniques using the above-mentioned copolymerization technique, The cause of the generation of lumpy polymer and poor dispersion, and as a result not only manufacturing problems,
In view of the problem that the quality of the obtained product becomes inadequate, the present inventors have earnestly studied a method for solving the problems of the prior art at the transition metal compound catalyst component stage.

As a result, a titanium catalyst component containing an alkenylsilane polymer and a method for producing the same were found, and when a catalyst in which the titanium catalyst component was combined with an organoaluminum compound and an electron donor was used, the above-mentioned conventional polyolefin was used. Not only is it possible to obtain a polyolefin having excellent transparency and crystallinity, which solves manufacturing problems and has extremely few voids.
The present invention has been completed by knowing that it has a remarkable effect also on the storage stability at high temperatures 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 provides a titanium catalyst component for olefin polymerization capable of producing a polyolefin having extremely high transparency and extremely high crystallinity and extremely low void generation with extremely high productivity, and a method for producing the titanium catalyst component. It is intended.

[Means for Solving Problems and Action of Invention]

 The present invention has the following configurations.

(1) Liquefied magnesium compound and halogen, halogenated hydrocarbon, halogen-containing titanium compound, halogen-containing zirconium compound, halogen-containing vanadium compound, one or more precipitants, halogen compounds, electron donors and tetravalent compounds. The solid product (I) obtained by catalyzing a titanium compound (T ₁ ) has the general formula: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Polymerization treatment with an alkenylsilane compound represented by A product (II) is obtained, which is obtained by reacting the solid product (II) with a tetravalent titanium halide compound (T ₂ ). (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group).
A titanium catalyst component for olefin polymerization, containing 0.1 to 99 wt% of titanium, magnesium, halogen and an electron donor as essential components.

(2) Liquefied magnesium compound and halogen, halogenated hydrocarbon, halogen-containing titanium compound, halogen-containing zirconium compound, halogen-containing vanadium compound, one or more precipitants selected from halogen compounds, electron donors and tetravalent compounds. The solid product (I) obtained by contacting with a titanium compound (T ₁ ) has the general formula: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Polymerization treatment with an alkenylsilane compound represented by 0.1% to 99% by weight of an alkenylsilane polymer, which is obtained by obtaining a product (II) and reacting the solid product (II) with a tetravalent titanium halide compound (T ₂ ). %, A method for producing a titanium catalyst component for olefin polymerization containing titanium, magnesium, halogen, and an electron donor as essential components.

The titanium catalyst component for olefin polymerization of the present invention is a titanium catalyst component for olefin polymerization containing an alkenylsilane polymer and containing titanium, magnesium, halogen and an electron donor as essential components. explain.

The term "liquefaction" of the magnesium compound as used in the present invention refers to the case where the magnesium compound itself becomes 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 also 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 methods (JP-A-58-19307, etc.) and the like, methods combining these may be mentioned.
Further, the organomagnesium compound having a C-Mg bond, to which the above-mentioned method cannot be applied, is soluble in ether, dioxane, pyridine and the like, and therefore it is used as a solution thereof or reacted with an organometallic compound, The general formula is M _P Mg _q R ⁴ _r R ⁵ _s (M is aluminum, zinc, boron, or beryllium atom, R ⁴ and R ⁵ 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 (Japanese Patent Laid-Open No. 50-139,885, etc.) and dissolved in a hydrocarbon solvent to be liquefied.

Furthermore, when metallic magnesium is used, a method of liquefying with an alcohol and an orthotitanate ester (Japanese Patent Laid-Open No. 51587/50, etc.) or reaction 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 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 an orthotitanic acid ester represented by Ti (OR ⁶ ) ₄ and a polytitanic acid ester represented by R ⁷ O—Ti (OR ⁸ ) (OR ⁹ ) _t OR ¹⁰ . Where R ⁶ , R ⁷ , R ⁸ ,
R ⁹ and R ¹⁰ are alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups 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, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-
In addition to monohydric alcohols such as propyl alcohol, n-butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and allyl alcohol, ethylene glycol and trimethylene. Polyhydric alcohols such as glycols and glycerin can also 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 precipitating agent (X ₁ ), the halogen compound (X ₂ ), the electron donor (B ₁ ) and the 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. Further, when the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, for example, alcohol, polysiloxane having a Si—H bond or the like 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 acids or organic 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, methanol, ethanol, n-
Alcohols such as propanol, i-propanol, n-butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol and glycerin, phenols such as phenol, cresol, xylenol and ethylphenol, Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other ketones, acetaldehyde, propionaldehyde, benzaldehyde and other aldehydes, formic acid, acetic acid, propionic acid, butyric acid, valeric acid and other carboxylic acids, methyl formate, methyl acetate, butyric acid Fats such as methyl, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, octyl acetate, phenyl acetate, ethyl propionate Aromatic monocarboxylic acid esters such as carboxylic acid esters, methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, phenyl anisate, monomethyl phthalate, dimethyl phthalate , Diethyl phthalate, di-n-propyl phthalate, di-n phthalate
-Propyl, mono-n-butyl phthalate, di-phthalate
n-butyl, di-i-butyl phthalate, di-n phthalate
-Hebutyl, 2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, Aromatic polycarboxylic acid esters such as di-i-butyl naphthalene dicarboxylic acid, ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid amide, benzoic acid amide, Acid amides such as toluic acid amide, acetic anhydride, maleic anhydride,
Acid anhydrides such as benzoic anhydride, phthalic anhydride and tetrahydrophthalic anhydride, amines such as ethylamine, tributylamine, aniline, pyridine, picoline, tetramethylethylenediamine, nitriles such as acetonitrile and benzonitrile, ethylphosphine, toluene Phosphines such as ethylphosphine, tri-n-butylphosphine, and triphenylphosphine; phosphites such as dimethylphosphite, triethylphosphite and triphenylphosphite; and phosphinites such as ethyldiethylphosphinite and ethylbutylphosphinite. And alkoxysilanes such as tetraethoxysilane and tetrabutoxysilane are used, and preferably aromatic monocarboxylic acid esters and aromatic polyvalent carboxylic acid ester alkoxysilanes, particularly Mashiku an aromatic polycarboxylic acid esters are used. One or more kinds of these electron donors (B ₁ ) are used, and the amount thereof is magnesium compound 1
It is 0.01 mol to 5 mol per mol.

Titanium compound (T ₁ ) required for preparation of solid product (I)
Is a general Ti (OR ¹¹ ) _4-u X _u (wherein R ¹¹ 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 include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride,
Propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, butoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibropoxy titanium dichloride, dibutoxy titanium dichloride , Diphenoxy titanium dichloride, diethoxy titanium dibromide, dibutoxy titanium dibromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride and the like. 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. Also,
Even when the 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 methods for contacting, for example, (X ₁ ) is added to a liquefied magnesium compound to precipitate a solid, and (X ₂ ), (B ₁ ), (T ₁ ) Method of contacting in any order. Liquefied magnesium compound and (B ₁ )
(X ₁ ) was added to the solution contacted with to precipitate a solid,
A method of bringing (X ₂ ) and (T ₁ ) into contact with the solid in any order.
After contacting the liquefied magnesium compound with (T ₁ ), (X ₃ ) 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 ) is obtained, but when a halogen-containing titanium compound is used as a depositing agent (X ₁ ), (X ₂ ) and (T ₁ ) are 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
5 minutes to 8 hours at each step at 10 kg / cm ² G, preferably 10
Minutes to 6 hours.

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 subjected to a polymerization treatment with an alkenylsilane compound in the presence of the organoaluminum compound (AL ₁ ) to obtain a solid product (II).

The polymerization treatment with the alkenylsilane compound is carried out by adding 100 g of an inert hydrocarbon solvent (D ₃ ) to 100 g of the solid product (I).
Add 5,000 ml of organoaluminum compound (AL ₁ ) 5 g to 5,000 g, reaction temperature 0 ° C. to 90 ° C. for 1 minute to 10 hours, reaction pressure is atmospheric pressure to 10 kg / cm ² G under conditions of alkenylsilane compound. Add 0.1 g to 100 kg and polymerize so that the content of the alkenylsilane polymer in the final titanium catalyst component will be 0.1% to 99% by weight. The content of the alkenylsilane polymer is
If it is less than 0.1% by weight, the effect of improving transparency and crystallinity of the α-olefin polymer produced using the obtained titanium catalyst component is insufficient, and if it exceeds 99% by weight, the improving effect is remarkable. It becomes 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 )
Has a general formula of AlR ¹² _m R ¹³ _m · X _{3- (m + m ′)} (where R
¹² and R ^{13 each} 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 and m ′ each 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 organoaluminums can 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 alkenylsilane compound used for the polymerization treatment has the general formula: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) As a specific example, vinyl Trimethylsilane, vinyltriethylsilane, vinyltrin-butylsilane, vinyldimethylcyclohexylsilane, vinyldimethylphenylsilane, allyltrimethylsilane, allyltriethylsilane, allyltripropylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, etc. can give.

Polymerization treatment with the alkenylsilane compound is performed as described above, and the solid product (II) is obtained by 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 an alkenylsilane 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 ¹¹ ) _4-uXu (wherein R ¹¹ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u represents an arbitrary number of 0 <u ≦ 4). A titanium oxide compound is used, and similar examples can be given, 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 Then, 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. Remove reactants or by-products.

Thus, the following equation of the present invention: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) 0.1% by weight to 99% by weight and titanium,
An olefin polymerized titanium catalyst component containing magnesium, a halogen, and an electron donor as essential components is obtained.

The titanium catalyst component containing the alkenylsilane polymer of the present invention obtained as described above can be used in the same manner as a known titanium catalyst component for olefin polymerization such as propylene.

The alkenylsilane polymer-containing titanium catalyst component comprises an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ )
It is used in the polymerization of olefin as a catalyst in combination with the above, or as a catalyst in which a small amount of olefin is preliminarily activated.

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. Further, the electron donor (B ₄ ) is preferably an organic acid ester, an organosilicon compound having a Si—O—C bond such as an alkoxysilane compound or an aryloxysilane compound, an ether, a ketone, an acid anhydride or an amine. Used. 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,
Amine with large steric hindrance such as 2,5,5-tetramethylpyrrolidine, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, Ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii-propoxysilane , Vinyltriacetoxysilane, and other organosilicon compounds having a Si—O—C bond.

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 used for the production of an olefin polymer. Used for. Polymerization methods for polymerizing olefins include slurry polymerization carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, and liquefied olefins such as liquefied propylene and liquefied butene-1. Bulk polymerization in monomer, ethylene,
There is a gas phase polymerization in which an olefin such as propylene is polymerized in a gas phase, or a method of stepwise combining two or more of the above. In any case, the polymerization temperature is room temperature (20 ℃)
~ 200 ℃, polymerization pressure is normal pressure (0kg / cm ² G) ~ 50kg / cm ² G,
It is usually carried out for 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-1,2-methyl-pentene-.
1 and other branched chain monoolefins, butadiene, isoprene, chloroprene and other diolefins, styrene, etc. Further, not only homopolymerization of each of these, but also in combination with other olefins, for example, propylene And ethylene, butene-1 and ethylene, propylene and butene-1, or three components such as propylene, ethylene, and butene-1 can be used for copolymerization, and the mixture is fed by multistage polymerization. It is also possible to carry out block copolymerization by changing the type of olefin.

〔The invention's effect〕

The main effect of the present invention is that when the titanium catalyst component of the present invention is used for the polymerization of olefins as a transition metal compound catalyst component for olefin polymerization, the generation of voids is extremely low with extremely high productivity, transparency and crystallinity. That is, a polyolefin having extremely high properties can be produced.

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 polyolefin are improved, and the number of generated voids is extremely small.

As will be apparent from the examples shown below, the internal haze of the press film of the polyolefin obtained using the titanium catalyst component of the present invention is higher than that of the polyolefin obtained using the titanium catalyst component containing no alkenylsilane polymer. about
It is 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 alkenylsilane polymer is not contained, and the crystallinity is remarkably improved and the flexural modulus is also remarkably increased (Example 1). 9 to Comparative Examples 1, 3, 5 to 10). Further, it is clear that the number of voids generated is significantly smaller than that of the polyolefin introduced with the alkenylsilane polymer by a method other than the present invention (see Examples 1 to 9 and Comparative Example 2).

The second effect of the present invention is an extremely high polymerization activity,
The particle shape is good and a highly stereoregular polyolefin can be obtained. Therefore, the catalyst removal step and the atactic polymer removal step can be omitted, and the polyolefin can be produced by a continuous polymerization method for a long period of time by a simpler process such as a gas phase polymerization method, which is extremely advantageous in process production. Is.

The third effect of the present invention is that the titanium catalyst component for olefin polymerization 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. The storage 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 olefin polymerization of the present invention is excellent in 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,
Prevention of line blockage troubles in the gas phase polymerization process,
It is extremely effective in preventing compressor troubles resulting from the mixing of finely divided olefin polymer into the circulating gas.

[Examples] Hereinafter, the present invention will be described with reference to Examples. The definitions of terms used in Examples and Comparative Examples and the measuring 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 ASTM D-1238 (L)
by. (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 described above, a polyolefin 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 with a differential scanning calorimeter at a temperature decrease rate of 10 ° C./min. (Unit: ° C.) Flexural modulus: Tetrakis [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxyphenyl) propionate]
0.5 parts by weight of methane and 0.5 parts by weight of calcium stearate were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, the granulated product was made into an injection molding machine with a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. to form a JIS type test piece, and the test piece had a humidity of 50% and a room temperature of 23
After left in a room at ℃ for 72 hours, the flexural modulus was measured according to JIS K7203. (Unit: kgf / cm ² ) Void: Polyolefin is granulated in the same manner as in the previous section, and the resulting granulated product is 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. 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 was added.
, Anhydrous magnesium chloride 480g, n-butyl orthotitanate 1.7kg and 2-ethyl-1-hexanol 1.95kg
Were mixed and heated to 130 ° C. for 1 hour while stirring to dissolve them to obtain a uniform solution. The homogenous 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, 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).

450 g of triethylaluminum and 145 g of diphenyldimethoxysilane whose total amount of the solid product (I) was maintained at 30 ° C.
After suspending it in hexane 10 containing 10 ml of hexane, 4.7 kg of allyltrimethylsilane was added, and the mixture was stirred at the same temperature for 2 minutes.
Polymerization was performed for a time. After the treatment, the supernatant was removed, n-hexane 6 was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain a polymerized solid product (II).
Got

The whole amount of the solid product (II) was mixed with titanium tetrachloride 5 dissolved in 1,2-dichloroethane 5, then 180 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. The liquid phase portion was removed by decantation at a temperature, 1,2-dichloroethane 5 and titanium tetrachloride 5 were added again, and the mixture was stirred at 100 ° C. for 2 hours, washed with hexane and dried to obtain a titanium catalyst component. The titanium catalyst component had a particle shape close to a sphere and contained 0.75% by weight of titanium and 75.0% by weight of polyallyltrimethylsilane.

(2) Preparation of pre-activated catalyst After a stainless steel reactor with an inclined blade and an internal volume of 30 was replaced with nitrogen gas, n-hexane 25, triethylaluminum 1.5 kg, diphenyldimethoxysilane 480 g and titanium obtained in (1) were used. 400 g of catalyst component was added at room temperature. The reactor was maintained at 30 ° C., and 450 Nl of ethylene was fed and reacted at the same temperature for 2 hours (per 1 g of titanium catalyst component,
After reacting 1.25 g of ethylene), unreacted ethylene was removed to obtain a preactivated catalyst.

(3) Polymerization of olefin After 20 kg of polypropylene powder of MFR2.0 was placed in a horizontal polymerization vessel of L / D = 3 equipped with a stirrer having an internal volume of 80, which was replaced with nitrogen, the above pre-activated catalyst slurry (titanium catalyst component) was used. In addition to the above, 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.
It was carried out continuously at 70 ° C. for 120 hours. During the polymerization period.
The polymer was continuously withdrawn from the polymerizer at 10 kg / hr so that the retained level of the polymer in the polymerizer was 60% by volume.
The polymer that was extracted subsequently contained propylene oxide.
It was obtained as a product powder after being contact-treated with nitrogen gas containing 0.2% by volume at 95 ° C. for 30 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), n-hexane 25 was added under a nitrogen atmosphere.
And 400 g of titanium catalyst component obtained in the same manner as in (1) above
I put it in. Subsequently, 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 / 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 allyltrimethylsilane. 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) Polymerization of propylene 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 the above (1) 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) In the reactor used in (2) of Example 1, n-heptane 20, 100 g of the titanium catalyst component obtained in (1) above, 400 g of diethylaluminum monochloride, 120 g of diphenyldimethoxysilane, 725 g of allyltrimethylsilane. In addition, the mixture was reacted at 40 ° C. for 2 hours (reaction of 2.9 g of allyltrimethylsilane per 1 g of titanium catalyst component). Then, it was washed with n-heptane and then filtered to obtain a solid. Further n-heptane 20,
After 400 g of diethylaluminum monochloride and 55 g of diphenyldimethoxysilane were added, 280 g of propylene was supplied and reacted at 30 ° C. for 1 hour (1.8 g of propylene was reacted per 1 g of titanium catalyst component).

(3) In place of the pre-activated 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 0.30 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 The polypropylene content was the same as in Example 1 (1) except that 2.4 kg of propylene was used instead of allyltrimethylsilane to polymerize the solid product (I).
A titanium catalyst component having 75.0% by weight and a titanium content of 0.75% by weight was obtained. Olefin polymerization was carried out in the same manner as in (2) and (3) of Example 1 except that this titanium catalyst component was used.

Comparative Example 4 and Examples 2 and 3 Titanium catalyst components having polyallyltrimethylsilane contents of 0.001% by weight, 16.7% by weight and 44.4% by weight, respectively, were used by changing the amount of allyltrimethylsilane used in (1) of Example 1. Got After that, the olefin 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.

Decane 6 in a stainless steel reactor with stirrer
, Magnesium-containing solid 1.0kg, orthotitanic acid n-
3.4 kg of butyl and 3.9 kg of 2-ethyl-1-hexanol were mixed and heated at 130 ° C. for 2 hours with stirring to dissolve the mixture into a uniform solution. The solution was brought to 70 ° C., 0.2 kg of p-toluate was added and reacted for 1 hour, then 0.4 kg of diisobutyl phthalate was added and reacted for another 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 hexane 10 containing 450 g of triethylaluminum and 75 g of methyl p-toluate kept at 25 ° C., and then allyltrimethylsilane was added.
3.6 kg was added, and polymerization was performed at the same temperature for 2 hours while stirring. After the treatment, the supernatant was removed and n-hexane 6 was added.
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.

0.4 kg of diisobutyl phthalate was added together with titanium tetrachloride 10 diluted with 1,2-dichloroethane 10 in the whole amount of the solid product (II), reacted with stirring at 100 ° C. for 2 hours, and then decanted at the same temperature. Remove the liquid phase part by
1,2-dichloroethane 10 and titanium tetrachloride 10 were added again, and the mixture was reacted at 100 ° C. for 2 hours while stirring. Then, the solid portion was collected by hot filtration, washed with purified hexane and dried to obtain a titanium catalyst component. Got The titanium catalyst component had a titanium content of 1.13% by weight and a polyallyltrimethylsilane content of 66.7%.
% By weight.

Then, 500 g of phenyltriethoxysilane instead of diphenyldimethoxysilane in (2) of Example 1,
In addition, a preactivated catalyst was obtained in the same manner except that the above titanium catalyst component was used as the titanium catalyst component.
Gas phase polymerization of propylene was carried out in the same manner as in (3).

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 allyltrimethylsilane.
Polymerization of propylene was performed.

Example 5 n-heptane 8 in a stainless steel reactor with stirrer
, Anhydrous magnesium chloride 1.0kg, orthotitanic acid n-
Mix 7.4 kg of butyl, raise the temperature to 90 ° C with stirring, and
It was heated and dissolved for a period of time to form a uniform solution. The homogeneous solution is then cooled to 40 ° C. and 1,500 ml of methyl hydrogen polysiloxane are added.
Was dropped to deposit a solid. This was washed with n-heptane to obtain an off-white solid. 500 g of the solid and n-heptane 7 were placed in a stainless steel reactor equipped with a stirrer. Next, 100 g of diisobutyl phthalate was added, 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
The reaction was carried out at 90 ° C for 1 hour. The solid is separated from the solution, n-
Washing with heptane gave a solid product (I).

2.5 mol of Agnesium atom equivalent solid product (I)
N-heptane 5 containing 200 g of triethylaluminum and 60 g of diphenyldimethoxysilane kept at 30 ° C.
Then, 2.2 kg of allyltrimethylsilane was added, and the mixture was polymerized at the same temperature for 2 hours while stirring. After the treatment, the solid was separated from the solution and washed with n-heptane to obtain a polymerized solid product (II).

The total amount of the solid product (II) is n-containing titanium tetrachloride 6.
Mix with heptane solution 12 followed by diheptyl phthalate
After adding 100 g and reacting at 50 ° C. for 2 hours, the mixture was washed with n-heptane, further 150 ml of titanium tetrachloride was added and washed at 90 ° C. to obtain a titanium catalyst component. The titanium content of the titanium catalyst component was 0.79% by weight, and the polyallyltrimethylsilane content was
It was 73.7% by weight.

Subsequently, in (2) of Example 1, 150 g of t-butyltriethoxysilane was used instead of diphenyldimethoxysilane.
Was obtained in the same manner as above except that the total amount of the above titanium catalyst component was used as the titanium catalyst component, and then vapor phase polymerization of propylene 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 allyltrimethylsilane.
Gas phase polymerization of propylene was performed.

Example 6 n-decane was added in a stainless steel reactor equipped with a stirrer.
2.5, anhydrous magnesium chloride 480g and 2-ethyl-
After heating 1.95 kg of 1-hexanol at 130 ° C. for 2 hours to dissolve it into a uniform solution, phthalic anhydride 11
1 g was added, and the mixture was further stirred and mixed at 130 ° C. to dissolve phthalic anhydride in the homogeneous solution. The homogeneous solution thus obtained was cooled to room temperature, and then the whole amount was dropped into titanium tetrachloride 10 kept at -20 ° C over 1 hour. After dropping, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and
When the temperature reached 10 ° C, the solid reacted under 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 in n-decane 10 containing the above, 4.7 kg of allyltrimethylsilane 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 parts of titanium tetrachloride, 350 g of diisobutyl phthalate was subsequently added, the mixture was reacted at 110 ° C. for 2 hours while stirring, and then the liquid phase was decanted at the same temperature. 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 reaction.

After completion of the reaction, the liquid phase part 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 titanium catalyst component. The titanium catalyst component comprised 0.75% by weight titanium and 75.0% by weight polyallyltrimethylsilane. Then,
0.385 mg atom / hr in terms of titanium atom of the above titanium catalyst component in a polymerization vessel equipped with a stirrer equipped with a two-stage turbine blade having an inner volume of 200, and 20% by weight of triethylaluminum.
8.5 g of n-hexane solution as triethylaluminum
/ hr, 20% by weight solution of diphenyldimethoxysilane in n-hexane as diphenyldimethoxysilane 3.0 g / h
r and n-hexane were continuously fed at 21 kg / hr.
Hydrogen was supplied so that the concentration in the gas phase was maintained at 0.25% by volume, and propylene was supplied so that the total pressure was maintained at 8 kg / cmG, 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 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 allyltrimethylsilane. Slurry polymerization of propylene was carried out in the same manner as in Example 6.

Example 7 A titanium catalyst component was obtained in the same manner as in Example 1 (1) except that 580 g of magnesium ethoxide and 3.3 kg of allyltrimethylsilane were used instead of anhydrous magnesium chloride. (2) of Example 1,
Polymerization of propylene was carried out in the same manner as in (3).

Comparative Example 8 Polymerization of propylene by obtaining a titanium catalyst component in the same manner as in Example 7 except that the solid product (I) is replaced with the solid product (II) without the polymerization treatment with allyltrimethylsilane. I went.

Example 8 In place of n-butyl orthotitanate in (1) of Example 1, 1.5 kg of n-butyl polytitanate (pentamer),
A titanium catalyst component was obtained in the same manner except that 2.9 kg of 3-butenyltrimethylsilane was used instead of allyltrimethylsilane. Then, the obtained titanium catalyst component was used to polymerize an olefin in the same manner as in (2) and (3) of Example 1.

Comparative Example 9 The solid product (I) was replaced by the solid product (I) in Example 8 without performing the polymerization treatment with 3-butenyltrimethylsilane.
I) A titanium catalyst component was obtained in the same manner as described above except that the equivalent was used to polymerize the olefin.

Example 9 The same procedure as in Example 6 was conducted except that the amount of allyltrimethylsilane used in obtaining the titanium catalyst component was 3.9 kg and ethylene was further supplied so that the concentration in the gas phase was 0.2% by volume during the olefin polymerization. And 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 allyltrimethylsilane, and propylene-ethylene was obtained. Copolymerization was performed.

[Brief description of drawings]

FIG. 1 is a flow sheet for explaining the method for producing the catalyst component of the present invention.

Claims (2)

[Claims] 1. A liquefied magnesium compound and a halogen, a halogenated hydrocarbon, a halogen-containing titanium compound,
A solid product (I) obtained by catalyzing one or more precipitants selected from halogen-containing zirconium compounds and halogen-containing vanadium compounds, halogen compounds, electron donors and tetravalent titanium compounds (T ₁ ), In the presence of an organoaluminum compound, the general formula (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Polymerization treatment with an alkenylsilane compound represented by The product (II) is obtained, and the solid product (II) is obtained by reacting a tetravalent titanium halide compound (T ₂ ). The following formula (Wherein n is an adjustment from 0 to 2 and R ¹ , R ² and R ³ represent an alkyl group, a cycloalkyl group or an aryl group).
A titanium catalyst component for olefin polymerization, containing 0.1 to 99 wt% of titanium, magnesium, halogen and an electron donor as essential components. 2. A liquefied magnesium compound and a halogen, a halogenated hydrocarbon, a halogen-containing titanium compound,
A solid product (I) obtained by contacting one or more precipitants selected from halogen-containing zirconium compounds and halogen-containing vanadium compounds, a halogen compound, an electron donor and a tetravalent titanium compound (T ₁ ), In the presence of an organoaluminum compound, the general formula (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Polymerization treatment with an alkenylsilane compound represented by 0.1% to 99% by weight of an alkenylsilane polymer, which is obtained by obtaining a product (II) and reacting the solid product (II) with a tetravalent titanium halide compound (T ₂ ). %, A method for producing a titanium catalyst component for olefin polymerization containing titanium, magnesium, halogen, and an electron donor as essential components.