JPH0780956B2 - Titanium catalyst component for α-olefin polymer production - Google Patents

Description

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

[Conventional technology and its problems]

A crystalline α-olefin polymer such as crystalline polypropylene is a so-called Ziegler-based polymer 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.
It is well known that it can be obtained by polymerizing an α-olefin with a Natta catalyst, and a method for obtaining an α-olefin polymer 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. Α-
In recent years, a method for polymerizing an olefin to produce an α-olefin polymer has been vigorously studied. (For example,
The applicant of the present invention 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, JP-A-62-104,812
JP-A-62-104,813 and the like disclose a method of obtaining an α-olefin polymer having a high stereoregularity and a good particle shape with a remarkably high polymerization activity.

However, although these improved methods have the advantages as described above, the obtained α-olefin polymer is translucent, which may impair the commercial value in the field of use, resulting in improved transparency. Was wanted.

On the other hand, attempts have also been made to improve the transparency of α-olefin polymers, for example, aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22,740). However, when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. In addition, when a benzylidene sorbitol derivative is used, there is a certain improvement in transparency, but there are problems such as strong odor during processing and bleeding of additives (embossing). It was

Styrene, o-methyl styrene, p-t-butyl styrene,
Method for carrying out multi-stage polymerization of 1-vinylnaphthalene and propylene and its composition (JP-A-62-1738, JP-A-62-227,911, JP-A-63-15,803, JP-A-63-15,803) 63-68,648 gazette), the inventors of the present invention produced polypropylene according to the method proposed by the present inventors. Since a polymer is produced, this method cannot be adopted in an industrial long-term continuous polymerization method, particularly in a gas phase polymerization method in which the polymerization of α-olefin 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 during the production of a transition metal catalyst component for propylene polymerization (Japanese Patent Laid-Open No. 63-69,809). No. gazette) has been proposed,
Since the proposed method requires a separate step of producing a pt-butylstyrene polymer, it is not only industrially disadvantageous, but also has the same problem of void formation in the film as in the above-mentioned prior art. Had.

The inventors of the present invention, when producing an α-olefin polymer with improved transparency, regarding a method of solving the problems such as the generation of a bulk polymer and the occurrence of voids in the film due to poor dispersion, which the conventional technique has. I studied hard.

As a result, a titanium catalyst component containing a crystalline polymer of a halogen-substituted styrene was found by a specific method, and when a catalyst in which this titanium catalyst component and an organoaluminum compound were used in combination, Not only is it possible to obtain an α-olefin polymer having excellent transparency and crystallinity, which can solve problems in producing an α-olefin polymer, has excellent dispersibility, and has extremely few voids, and the titanium catalyst The inventors of the present invention have found that there is a remarkable effect on the storage stability of the components at high temperatures of 35 ° C. or higher, and on the attrition resistance in the production equipment during the large-scale production of the titanium catalyst component.

The present invention provides a titanium catalyst component for producing an α-olefin polymer capable of producing an α-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. The purpose is to do.

[Means for solving the problem]

 The present invention has the following configurations.

(1) The following equation, (Wherein X represents halogen, R ¹ represents hydrogen or an alkyl group), and contains 0.01% to 99% by weight of a halogen-substituted styrene crystalline polymer composed of a repeating unit represented by the following formula. The final solid product (II
I) a titanium catalyst component for producing an α-olefin polymer.

Liquefied magnesium compound and halogen or halogen compound, electron donor and titanium compound represented by the general formula Ti (OR ¹¹ ) _4-u X _u (T ₁ ) (wherein R ¹¹ is an alkyl group, a cycloalkyl group, Or an aryl group, X represents halogen, and u is an arbitrary number of 0 <u ≦ 4, and the solid product (I) obtained by the following formula in the presence of an organoaluminum compound: , (In the formula, X is halogen and R ¹ is hydrogen or an alkyl group.) Polymerization treatment is carried out with halogen-substituted styrenes to obtain a solid product (II), and the solid product (II) is halogenated. Final solid product (III) obtained by reacting titanium oxide compound (T ₂ ).

(2) As the organoaluminum compound, the general formula is A1R ² _m R
³ _{m ′} X _{3- (m + m ′)} (wherein R ² and R ³ 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 ′ Represents an arbitrary number of 0 <m + m '≦ 3.) The catalyst component according to the above item 1, wherein the organoaluminum compound represented by the formula is used.

The titanium catalyst component for producing an α-olefin polymer of the present invention has the following formula: (In the formula, X represents halogen and R ¹ represents hydrogen or an alkyl group.) A crystalline polymer of halogen-substituted styrenes (hereinafter, abbreviated as halogen-substituted styrene polymer). And a titanium catalyst component for producing an α-olefin polymer containing titanium, magnesium, a halogen, and an electron donor as essential components.

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 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 method (Japanese Patent Application Laid-Open No. 58-19,307, etc.) and the like, there may be mentioned a method in which these are combined.
Further, it is not possible to apply the above method, for the organomagnesium compound having a C-Mg bond, ether,
Since it is soluble in dioxane, pyridine, etc., it can be used as a solution of these or can be reacted with an organometallic compound to give a compound of the general formula M _p Mg _q R ⁴ _r R ⁵ _s (M is an aluminum, zinc, boron, or beryllium atom). , R ⁴ , R ⁵ are hydrocarbon residues, p, q,
There is a relationship of r + s = vP + 2q where r, s> o, v are the valences of M. A complex compound represented by the formula
-139,885 gazette), it can be liquefied by dissolving in a hydrocarbon solvent.

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. , 0.1 mol to 2 mol of titanic acid ester, 0.1 mol to 5 mol of alcohol, and 0.1 to 5 liter of solvent (D ₁ ) are used to mix the respective components in an arbitrary addition order, and the suspension is stirred. Heating is performed 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 ⁶ ) ₄ and R ⁷ O—Ti (OR ⁸ ) (OR ⁹ _t O
An example is polytitanate represented by R ¹⁰ .
Here, 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 forthotitanate, 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, pentanol, hexanol, octanol, 2-ethylhexanol, and allyl alcohol, ethylene glycol,
Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, carbon number 4 ~
Ten saturated aliphatic alcohols are preferred.

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.

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 acids 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 naphthalenedicarboxylate, methyl ether, ethyl ether, isopropyl Ethers such as ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc., acetic acid amides, benzoic acid amides, acid amides such as toluic 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, ethyldiethylphosphinite, ethylbutylphosphinite and the like. Alkoxysilanes such as phosphinites, tetraethoxysilane and tetrabutoxysilane are used, preferably aromatic monocarboxylic acid esters, aromatic polyvalent carboxylic acid esters, alkoxysilanes, and particularly preferably aromatic polycarboxylic acid esters. Divalent 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 a general formula Ti (OR ¹¹ ) _4-u X _u (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. And a orthotitanic acid ester or polytitanic acid ester which has been mentioned at the time of liquefaction of the above-mentioned magnesium compound are 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 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-mentioned method was treated with the following formula in the presence of an organoaluminum compound (AL ₁ ). (In the formula, X represents halogen and R ¹ represents hydrogen or an alkyl group.) Polymerization treatment with halogen-substituted styrenes (hereinafter sometimes abbreviated as halogen-substituted styrenes) produces a solid. Get the object (II).

Polymerization with halogen-substituted styrenes is carried out by adding 100 ml of an inert hydrocarbon solvent (D ₃ ) to 100 g of the solid product (I).
5,000 ml, organoaluminum compound (AL ₁ ) 0.5 g to 5,000 g
0.01 to 100 kg of halogen-substituted styrenes at a reaction temperature of 0 to 90 ° C. for 1 minute to 10 hours and a reaction pressure of atmospheric pressure to 10 kg / cm ² G to give a final solid product. (II
I), that is, the polymerization is carried out so that the content of the halogen-substituted styrene polymer in the titanium catalyst component of the present invention is 0.01% by weight to 99% by weight. The content of the halogen-substituted styrene polymer is
If it is less than 0.01% 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 )
The general formula ^{_{A1R 2 m R 3 m 'X}} 3- (m + m') ( wherein R ^2, R ³ is an alkyl group, a cycloalkyl group, a hydrocarbon group or an alkoxy group and an aryl group, X is a halogen , And m and m'represent any number of 0 <m + m'≤3.)
And specific examples thereof include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, and tri-i.
-Butyl aluminum, tri-n-hexyl aluminum, tri-i-hexyl aluminum, tri-2-methylpentyl aluminum, tri-n-octyl aluminum,
Trialkyl aluminums such as tri-n-decyl aluminum, diethyl aluminum monochloride, di-n-
Propyl aluminum monochloride, di-butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide,
Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i
Examples include monoalkylaluminum dihalides such as -butylaluminum dichloride, and other alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum. These organoaluminum compounds are 2
It is also possible to use a mixture of more than one type.

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

The halogen-substituted styrenes used in the polymerization treatment have the following formula: (In the formula, X represents any halogen of Cl, Br, F, and I, and R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms.). Specific examples include 2-ethyl-4-chlorostyrene, 2-methyl-4-fluorostyrene, o-fluorostyrene and p-fluorostyrene.

The solid-state product (II) is obtained by carrying out the polymerization treatment with halogen-substituted styrenes as described above 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 halogen-substituted styrene polymer. The titanium halide compound (T ₂ ) is represented by the general formula given as an example of the titanium compound (T ₁ ) necessary for preparing the solid product (I) described above.
Ti (OR ¹¹ ) _4-u X _u (wherein R ¹¹ 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 solid product (III) is obtained by removing the reactants or by-products.

Thus, the halogen-substituted styrene polymer of the present invention can be added to 0.01
A solid product (III), which contains titanium, magnesium, halogen, and an electron donor as essential components, that is, a titanium catalyst component for producing an α-olefin polymer of the present invention is obtained. .

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

The halogen-substituted styrene polymer-containing titanium catalyst component was combined with an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ) to form a catalyst, or preliminarily activated by polymerizing a small amount of α-olefin. Used as a catalyst in α-olefin polymerization.

As the organoaluminum compound (AL ₂ ) used for the polymerization of α-olefin, the same organoaluminum compound as (AL ₁ ) used for obtaining the titanium catalyst component of the present invention can be used. 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,
Amines with large steric hindrance such as 2,2,5,5-tetramethylpyrrolidine, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxy Silane, ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii- Examples thereof include organosilicon compounds having a Si—OC bond such as propoxysilane and vinyltriacetoxysilane.

The amount of each catalyst component used is the same as in the case of ordinary α-olefin polymerization, but specifically, to 1 g of the titanium catalyst component, 0.05 to 500 g of an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ) About 0.01g to 200g.

Further, as the α-olefin used for preliminary activation,
Linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1;
4-methyl-pentene-1,2-methyl-pentene-1
And branched-chain monoolefins.

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

The polymerization mode of the α-olefin using the above catalyst is not limited, and it can be suitably carried out not only in liquid phase polymerization such as slurry polymerization and bulk polymerization but also in gas phase polymerization.

For slurry polymerization or bulk polymerization, titanium catalyst component and organoaluminum compound (AL ₂ ) and electron donor (B ₄ )
Although the effect obtained by using a combination of the above-mentioned catalysts is sufficiently exhibited, in the case of gas phase polymerization, a catalyst obtained by reacting an α-olefin with preactivation is preferable. When performing gas phase polymerization subsequent to slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, at the time of gas phase polymerization, the reaction of α-olefin has already been performed, the latter catalyst The same effect can be 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 liquefied α-olefins such as liquefied propylene and liquefied butene-1, It can be carried out in gaseous ethylene or 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 α-olefin polymer to be polymerized. The polymer particles to be coexisted are 0 to 1 g of the titanium catalyst component.
It is in the range of 5,000g.

The solvent or α-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, filtration or the like, or the solid product
Solvents can also be added to suspend them in amounts not exceeding 80 l / g.

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 α-olefin is α-olefin. Used in the production of polymers. As the polymerization method for polymerizing α-olefin,
As described above, in slurry polymerization conducted in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, in a liquefied α-olefin monomer such as liquefied propylene or liquefied butene-1. Bulk polymerization conducted, α-of ethylene, propylene, etc.
There is a gas phase polymerization in which an olefin is polymerized in a gas phase, or a method of stepwise combining two or more of the above.
In either case, the polymerization temperature is room temperature (20 ° C) to 200 ° C, the polymerization pressure is normal pressure (0 kg / cm ² G) to 50 kg / cm ² G, and usually 5 minutes to 2 minutes.
It is carried out for about an hour.

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 α-olefin used for the polymerization is ethylene,
Propylene, butene-1, hexene-1, octene-1
Linear monoolefins such as 4-methylpentene-
Branched chain monoolefins such as 1,2-methyl-pentene-1 and diolefins such as butadiene, isoprene, and chloroprene, and the like, and not only homopolymerization of each of these, but also other α- It is also possible to carry out the copolymerization in combination with olefin, for example, propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or three components such as propylene, ethylene and butene-1. Also, block copolymerization can be carried out by changing the type of α-olefin fed in multistage polymerization.

[Action]

The α-olefin polymer obtained by using the titanium catalyst component of the present invention contains a highly stereoregular halogen-substituted styrene polymer in an extremely dispersed state. The nucleation action of the coalescence reduces the spherulite size of the α-olefin polymer and promotes crystallization, and as a result, the transparency and crystallinity of the entire α-olefin polymer are increased.

Further, by using the titanium catalyst component of the present invention, α
Since the halogen-substituted styrenic polymer introduced into the olefin polymer is a 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 the titanium catalyst component of the present invention is α-
When used as a transition metal compound catalyst component for the production of olefin polymers in the polymerization of α-olefins, it produces an α-olefin polymer having extremely high productivity and extremely few voids, and extremely high transparency and crystallinity. It is possible.

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

The first effect of the present invention is that when the product of the present invention is used for α-olefin polymerization, both transparency and crystallinity of the obtained α-olefin polymer are improved and the number of voids is extremely small. Is.

As is apparent from the examples shown below, the internal haze of the press film of the α-olefin polymer obtained by using the titanium catalyst component of the present invention does not contain a halogen-substituted styrene polymer, and the titanium catalyst component is used. The resulting α-olefin polymer has a ratio of about 1/4 to 3/7, which is extremely high transparency.

In addition, the crystallization temperature was increased by about 6 ° C to 9 ° C as compared with the case where the halogen-substituted styrene polymer was not contained, and the crystallinity was remarkably improved and the flexural modulus was also remarkably increased. 1-9, Comparative Examples 1, 5-10).

Further, it is clear that the number of voids generated is significantly smaller than that of the α-olefin polymer introduced with the styrene polymer by the method other than the present invention (Examples 1 to 1).
9, see Comparative Examples 2 and 3).

The second effect of the present invention is an extremely high polymerization activity,
That is, an α-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 α-olefin polymer can be produced by a long-term continuous polymerization method by a simpler process such as a gas phase polymerization method. It is extremely advantageous in production.

The third effect of the present invention is that the titanium catalyst component for producing an α-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. 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 producing an α-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 α-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 α-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 fine powder α-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 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 conditions of α-olefin polymer powder thickness 150μ
After coating liquid paraffin on both surfaces of the film, 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: 100 parts by weight of α-olefin polymer powder, tetrakis [methylene-3 (3 ', 5'-di-
t-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 α-olefin polymer was granulated in the same manner as in the previous section, and the resulting granulated product was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine. , 1mm thick with 20 ℃ cooling roll
Created a sheet of. The sheet was heated with hot air of 150 ° C. for 70 seconds and stretched 7 times in both the longitudinal and transverse directions using a biaxial stretching machine to obtain a biaxially stretched film having a thickness of 20 μm. The film was observed with an optical microscope, and the number of voids having a diameter of 10 μm or more was measured, and less than 20 per 1 cm ² was indicated by ◯, 20 or more and less than 50 by Δ, and 50 or more 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 l of hexane containing 2-methyl-4-
Fluorostyrene (4.8 kg) was added, and polymerization was carried out at the same temperature for 2 hours while stirring. 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, followed by addition of 180 g of diisobutyl phthalate and reaction with stirring at 100 ° C. for 2 hours. The liquid phase was removed by decantation at the same 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 was obtained. The titanium catalyst component had a particle shape close to a sphere, and contained 1.76% by weight of titanium and 41.2% by weight of a crystalline 2-methyl-4-fluorostyrene 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) 170 g of catalyst component was added at room temperature. The reactor was kept at 30 ° C., and 160 Nl of ethylene was fed at the same temperature for 2 hours to react (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 α-olefin After 20 kg of polypropylene powder of MFR2.0 was put into a horizontal polymerizer of L / D = 3 equipped with a stirrer having an internal volume of 80 l and replaced with nitrogen, the above preactivated catalyst slurry (titanium catalyst) was used. In addition to the components, triethylaluminum and diphenyldimethoxysilane were continuously supplied at 0.286 mg atom / hr in terms of titanium atom. The concentration in the gas phase is 0.15
Hydrogen was supplied so as to maintain the 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 performed 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 170 g of titanium catalyst component obtained in the same manner as in (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) The solid product (I) in Example 1 (1) was mixed with 2
A titanium catalyst component was obtained in the same manner except that the solid product (II) equivalent was obtained without polymerizing with -methyl-4-fluorostyrene.

(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 placed in the reactor used in (2) of Example 1, and then p -T-butylstyrene
108g was added and reacted at 40 ° C for 2 hours (titanium catalyst component
0.7 g reaction of pt-butylstyrene 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 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 had to be stopped 9 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, and 385 g of 3 kg of pt-butylstyrene polymer obtained was pulverized in a vibration mill for 5 hours and then homogenized as described above. 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-methyl-4-fluorostyrene used in the polymerization treatment in (1) of Example 1, the crystalline 2-methyl-4-fluorostyrene weight was changed. Titanium catalyst components having a combined content of 0.001% by weight, 4.8% by weight and 23.1% by weight were obtained. After that, propylene was polymerized in the same manner as in (2) and (3) of Example 1.

Example 4 1.7 kg of aluminum trichloride (anhydrous) and 0.6 kg of magnesium hydroxide were reacted in a vibration mill while pulverizing at 250 ° C. for 3 hours, and 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., 1.8 kg of 2-methyl-4-fluorostyrene was added, and the mixture was stirred. However, the polymerization treatment was carried out at the same temperature for 2 hours. After the treatment, remove the supernatant and n-
The procedure of adding 6 liters of hexane and removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (I
I) got.

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 portion was removed by decantation at the same temperature, 10 l of 1,2-dichloroethane and 10 l of titanium tetrachloride were again added and stirred. While reacting at 100 ° C. for 2 hours, hot filtration was performed to collect a solid portion, which was washed with purified hexane and dried to obtain a solid product (III) as a final titanium catalyst component. The titanium content of the titanium catalyst component was 2.72% by weight, and the content of crystalline 2-methyl-4-fluorostyrene polymer was 20.0%.
% 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 In Example 4, the solid product (I) was treated with 2-methyl-4.
-A titanium catalyst component was obtained and propylene was polymerized in the same manner except that the solid product (II) equivalent was obtained without performing a polymerization treatment with fluorostyrene.

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).

2.5 mol of the solid product (I) in terms of magnesium atom
Was suspended in 5 l of n-heptane containing 200 g of triethylaluminum and 60 g of diphenyldimethosisilane kept at 30 ° C., and then 2.2 kg of o-fluorostyrene was added,
Polymerization was carried out 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 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 1.88% by weight, and the crystalline o-fluorostyrene polymer content was 37.5% 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 equivalent of the solid product (II) without being polymerized with o-fluorostyrene.
Gas phase polymerization of propylene was performed.

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 in 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.
Suspended in 10 l of n-decane containing 2-methyl-4
-4.3 kg of fluorostyrene was added, and polymerization was carried out at the same temperature for 2 hours while stirring. After the treatment, the solid was separated from the solution and washed with hexane to obtain a solid product (II) subjected to the polymerization treatment. The whole solid product (II) was mixed with 10 l of titanium tetrachloride, followed by diisobutyl phthalate 35
After adding 0 g and reacting at 110 ° C for 2 hours with stirring, the liquid phase part was removed by decantation at the same temperature, 1,000 ml of titanium tetrachloride was added again, and the mixture was heated at 110 ° C for 2 hours for reaction. It was

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 1.82 wt% titanium and 39.4 wt% crystalline 2-methyl-4-fluorostyrene polymer. Subsequently, 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 having an inner volume of 200 l to prepare a 4.0 wt% n-hexane suspension, and the suspension was 0.392 mg atom / hr in terms of titanium atom, 8.5 g / hr in triethylaluminum, and diphenyldimethoxysilane
N-Hexane was continuously supplied at 21 kg / hr from the same pipe at 3.0 g / hr and from another pipe. Furthermore, hydrogen is added so that the concentration in the gas phase of the polymerization vessel remains 0.25% by volume, and the total pressure is 8 kg / cm.
Slurry polymerization of propylene was continuously carried out at 70 ° C. for 120 hours by supplying propylene so as to maintain ² G. During the polymerization period, the holding level of slurry in the polymerization vessel is
The slurry was continuously withdrawn from the polymerization reactor to a flash tank having an internal volume of 50 l so that the volume became 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 is separated from the solvent by a centrifuge and then dried by a drier to obtain a product powder.
It was continuously obtained at 10 kg / hr.

Comparative Example 7 Obtained in the same manner as in Example 6 except that the solid product (I) was changed to the solid product (II) equivalent without the polymerization treatment with 2-methyl-4-fluorostyrene. Slurry polymerization of propylene was carried out in the same manner as in Example 6 using the titanium catalyst component.

Example 7 Obtained in the same manner as in Example 1 (1) except that 580 g of magnesium ethoxide was used instead of anhydrous magnesium chloride, and 5.6 kg of o-fluorstyrene was used instead of 2-methyl-4-fluorostyrene. Solid product (II
I) was used as the final titanium catalyst component and the rest of Example 1
Gas phase polymerization of propylene was carried out in the same manner as in (2) and (3) above.

Comparative Example 8 A titanium catalyst component was obtained in the same manner as in Example 7 except that the solid product (I) was replaced with the solid product (II) without the polymerization treatment with o-fluorstyrene. Was polymerized.

Example 8 In (1) of Example 1, 1.2k of n-butyl polytitanate (pentamer) was used instead of n-butyl orthotitanate.
A titanium catalyst component was obtained in the same manner except that 0.9 kg of p-fluorostyrene was used instead of 2-methyl-4-fluorostyrene. 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-fluorostyrene. Was polymerized.

Example 9 In Example 6, the amount of 2-methyl-4-fluorostyrene used was 4.0 kg when the titanium catalyst component was obtained, and ethylene was further added so that the concentration in the gas phase during propylene polymerization was kept at 0.2% by volume. Propylene-
Ethylene copolymerization was performed.

Comparative Example 10 A titanium catalyst component was prepared in the same manner as in Example 9 except that the solid product (I) was changed to the solid product (II) equivalent without the polymerization treatment with 2-methyl-4-fluorostyrene. To obtain propylene-ethylene copolymerization.

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 manufacturing process diagram (flow chart) for explaining the manufacturing process of the present invention.

Claims (2)

[Claims] 1. The following equation, (Wherein X represents halogen, R ¹ represents hydrogen or an alkyl group), and contains 0.01% to 99% by weight of a halogen-substituted styrene crystalline polymer composed of a repeating unit represented by the following formula. The final solid product (II
I) a titanium catalyst component for producing an α-olefin polymer. Liquefied magnesium compound and halogen or halogen compound, electron donor and titanium compound represented by the general formula Ti (OR ¹¹ ) _4-u X _u (T ₁ ) (wherein R ¹¹ is an alkyl group, a cycloalkyl group, Or an aryl group, X represents halogen, and u is an arbitrary number of 0 <u ≦ 4), and the solid product (I) obtained in the following formula in the presence of an organoaluminum compound: , (In the formula, X represents halogen and R ¹ represents hydrogen or an alkyl group.) Polymerization treatment was carried out with halogen-substituted styrenes to give a fixed product (II), and the solid product (II) was halogenated. Final solid product (III) obtained by reacting titanium oxide compound (T ₂ ). 2. An organoaluminum compound having the general formula
A1R ² _m R ³ _{m ′} X _{3- (m + m ′)} (In the formula, R ² and R ³ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; The catalyst component according to claim 1, wherein the organoaluminum compound represented by m and m'represents an arbitrary number of 0 <m + m'≤3.