JP2671018B2 - Titanium catalyst component for α-olefin polymerization and method for producing the same - Google Patents

Description

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

[Conventional technology and its problems]

Crystalline α-olefin polymers such as crystalline polypropylene include transition metal compounds of Groups IV to VI of the periodic table and I to III.
It is well known that it can be obtained by polymerizing an α-olefin with a so-called Ziegler-Natta catalyst, which is composed of an organometallic compound of a Group 3 metal, and has a high polymerization activity and a high stereoregular α-olefin weight. Ways to get coalesced have 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, a method for producing an α-olefin polymer by polymerizing an α-olefin with a catalyst that has been combined has been vigorously studied. (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-62-1.
04,810 PR, JP 62-104,811 PR, JP 62-1
In 04,812 public relations, JP 62-104,813 public relations, etc.,
Disclosed is a method for 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 application, and the improvement in transparency is not achieved. Was desired.

On the other hand, attempts have 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. ,
Also, when a benzylidene sorbitol derivative is used, although a certain improvement in transparency is observed,
There were problems such as strong odor during processing and bleeding of additives (embossing).

As a means for improving the above-mentioned problems when adding the nucleating agent, a method for carrying out multi-stage polymerization of styrene, o-methylstyrene, pt-butylstyrene, 1-vinylnaphthalene and propylene and a composition thereof (special feature (Kaisho 62-1,738, JP 62-227,911, JP 63-15803, JP 63-68,648) have been proposed, the present inventor according to the method of the proposal In addition, when polypropylene is produced, not only the polymerization activity of propylene is lowered by any method, but also a lump polymer is produced. Therefore, an industrial long continuous polymerization method, particularly α-olefin polymerization It was a method that cannot be adopted in the gas phase polymerization method performed in the gas phase. Furthermore, a film produced using the obtained polypropylene had many voids, which impaired commercial value.

As a similar technique, a method of polymerizing propylene using the catalyst component obtained by adding a pt-butylstyrene polymer during the course of the formation of the transition metal catalyst component for propylene polymerization (Japanese Patent Laid-Open No. 63-69,809). However, since the proposed method requires a separate step of producing a pt-butylstyrene polymer, it is not only industrially disadvantageous, but also the above-mentioned prior art. There was a similar problem of void formation in the film.

The present inventors have found that, when producing an α-olefin polymer having improved transparency, a void in a film caused by poor formation or poor dispersion of a bulk polymer in the prior art utilizing a polymer of styrenes. We studied hard to solve problems such as occurrence.

As a result, a titanium catalyst component containing a dimethylstyrene polymer was found by a specific method, and when a catalyst in which the titanium catalyst component was combined with an organoaluminum compound was used, the conventional α-olefin polymer as described above was used. Solves the problem of production, and has excellent dispersibility and extremely few voids, not only an α-olefin polymer having excellent transparency and crystallinity can be obtained, but the titanium catalyst component of 35 ° C or higher Storage stability at high temperature at
The present invention has been completed by knowing that the titanium catalyst component has a remarkable effect also on the attrition resistance in the production apparatus during the large-scale production.

The present invention provides an α-olefin polymer titanium catalyst component 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.

[Means to solve the problem]

 The present invention has the following configuration.

(1) 0.01% to 99% by weight of dimethylstyrene polymer
Containing one or more titanium compounds selected from butyl orthotitanate, n-butyl polytitanate or titanium tetrachloride, magnesium chloride, a reaction product of magnesium hydroxide and aluminum chloride, or one or more selected from magnesium ethoxide. A titanium catalyst component for α-olefin polymerization, which contains a magnesium compound, chlorine (existing in the compound), triethylaluminum and an electron donor as essential components.

(2) One kind of dimethylstyrene polymer selected from 2,4-dimethylstyrene polymer, 2,5-dimethylstyrene polymer, 3,4-dimethylstyrene polymer, and 3,5-dimethylstyrene polymer The titanium composition according to item 1, which is the above-mentioned dimethylstyrene polymer.

(3) A compound obtained by liquefying one or more compounds selected from magnesium chloride, magnesium hydroxide or magnesium ethoxide and a depositing agent (only when the titanium compound is not a halogen compound), a halogen compound (titanium compound, depositing agent (Neither is a halogen compound), an electron donor and n-butyl orthotitanate,
The solid product (I) obtained by contacting one or more titanium compounds (T ₁ ) selected from n-butyl polytitanate or titanium tetrachloride is polymerized with dimethylstyrene in the presence of triethylaluminum to give a solid. To obtain the product (II),
The solid product (II) is reacted with titanium tetrachloride to contain 0.01% to 99% by weight of a dimethylstyrene polymer, and titanium, magnesium, a halogen and an electron donor are essential components. Process for producing titanium catalyst component for olefin polymerization.

(4) As dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene,
And the production method according to the above item 3, wherein one or more kinds of dimethylstyrene selected from 3,5-dimethylstyrene are used.

The α-olefin polymerization titanium catalyst component of the present invention contains a dimethylstyrene polymer, and is a titanium catalyst component for α-olefin polymerization containing titanium, magnesium, halogen, and an electron donor as essential components. The manufacturing method will be described.

The “liquefaction” of the magnesium compound referred to in the present invention
Means that the magnesium compound itself becomes liquid,
When it is soluble in a solvent and forms a solution,
As a result of reacting with another compound or forming a complex, the compound is solubilized in a solvent to form a solution. Further, the solution may not only be completely dissolved, but also contain a colloidal or semi-dissolved substance.

As the magnesium compound to be liquefied, any compound can be used as long as it can be in the “liquefied” state, and for example, magnesium dihalide, diethoxymagnesium, magnesium hydroxide can be used. Further, these magnesium compound or metallic magnesium may be a reaction product with an electron donor, a silicon compound or an aluminum compound.

Known methods are used for liquefying the magnesium compound. For example, a method of liquefying a magnesium compound with an alcohol, an aldehyde, an amine, or a carboxylic acid (Japanese Patent Laid-Open No. 58-811), a method of liquefying an altotitanate ester (Japanese Patent Laid-Open No. 54-402,93). (Public relations, etc.), a method of liquefying with a phosphorus compound (JP-A-58-19307)
No. Public Relations, etc.) and the like, methods combining these, etc. (Publication No. 58-19307, etc.), etc., and methods combining these. 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 ³ _r R ⁴ _s (M is aluminum, zinc, boron, or beryllium atom, R ³ , R ⁴
Is a hydrocarbon group, where p, q, r, s> 0, and v are valences of M, there is a relation of r + s = 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 Laid-Open Patent Publication 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.

Among the methods for liquefying a magnesium compound as described above, for example, the case where magnesium chloride is dissolved in a hydrocarbon solvent (D ₁ ) using a titanate and an alcohol will be described. Using 0.1 mol to 2 mol of titanate, 0.1 mol to 5 mol of alcohol, and 0.1 to 5 solvent (D ₁ ), the respective components are mixed in any order, and the suspension is stirred. Heat 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, it is 10 minutes to 5 hours.

Examples of the titanic acid ester include orthotitanic acid ester represented by Ti (OR ⁵ ) ₄ and R ⁶ [O—Ti (OR ⁷ ) (O
R ⁸ )] _t OR ⁹ is a polytitanate ester.
Wherein ^{R 5, R 6, R 7} , R 8, and R ⁹ is cycloalkyl group of the alkyl group or 3 to 20 carbon atoms, having 1 to 20 carbon atoms, t is a number from 2 to 20.

Specifically, orthotitanate such as n-butyl orthotitanate and polytitanate such as n-butyl polytitanate can be used. The amount of polytitanate used may be equivalent to orthotitanate in terms of orthotitanate.

As the alcohol, aliphatic saturated and unsaturated alcohols can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i
-Propyl alcohol, n-butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and monohydric alcohols such as allyl alcohol, ethylene glycol, Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, an aliphatic saturated alcohol having 4 to 10 carbon atoms is 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 carbon hydrogens such as dichloroethane, 1,1,2-trichloroethane, chlorobenzene and 0-dichlorobenzene. Among them, aliphatic hydrocarbons are preferred.

The solid product (I) is obtained by contacting the liquefied magnesium compound with the precipitant (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 halogens, 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 organic magnesium compound, a compound having active hydrogen, for example, an alcohol, a polysiloxane having a Si—H bond, or the like can also be used. These precipitants (X ₁ )
Is used in an amount of 0.1 mol to 50 mol per 1 mol of the magnesium compound.

Examples of the halogen compound (X ₂ ) include a halogen and a compound containing a halogen, and the same halogenating agents as those mentioned as examples of the precipitating agent can be used. When used, a new use of the halogen compound (X ₂ ) is not necessarily required. The amount of halogen compound (X ₂₎ is 0.1 mol to 50 mol, relative to 1 mol of the magnesium compound.

Examples of the electron donor (B ₁ ) include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides, ammonia, amines, and nitriles. And a nitrogen-containing electron donor such as isocyanate, and a phosphorus-containing electron donor such as phosphine, phosphite, and phosphinite.

Specifically, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol and glycerin, phenol, Cresol, xylenol, phenols such as ethylphenol, acetone, methylethylketone, methylisobutylketone, acetophenone, ketones such as benzophenone, acetaldehyde, propionaldehyde, aldehydes such as benzaldehyde, formic acid, formic 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 carboxylic 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-butary phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, 2-ethylhexyl phthalate, phthalate Acid di-n-octyl, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate,
Dibutyl terephthalate, di-i-naphthalenedicarboxylic acid
-Aromatic polycarboxylic acid esters such as butyl, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran,
Anisole, ethers such as diphenyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, acetic anhydride, maleic anhydride, benzoic acid anhydride, phthalic anhydride, terrahydrophthalic acid anhydride, etc., Ethylamine, tributylamine, aniline, pyridine,
Amines such as picoline and tetramethylethylenediamine, nitriles such as acetonitrile and benzonitrile,
Phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, and triphenylphosphine; phosphites such as dimethylphosphite, triethylphosphite and triphenylphosphite; ethyldiethylphosphinite, ethylbutylphosphinites Alkoxysilanes such as phosphinites, tetraethoxysilane, and tetrabutoxysilane are used, and preferably aromatic monocarboxylic acid esters, aromatic polyvalent carboxylic acid esters, alkoxysilanes,
Particularly preferably, aromatic polycarboxylic acid esters are used.

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

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

Specific examples of the titanium halide compound include titanium tetrachloride and the like.

As the orthotitanate and the polytitanate, the same ones as described above can be mentioned. One or more kinds of these titanium compounds (T ₁ ) are used. However, when a titanium halide compound is used as the titanium compound (T ₁ ), since it has halogen, one precipitant (X ₁ ) and a halogen compound are used. The use of (X ₂ ) is optional.

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

The above liquefied magnesium compound, precipitating agent (X ₁ ), halogen compound (X ₂ ), electron donor (B ₁ ) and titanium compound (T ₁ ) are brought into contact with each other with stirring to give a solid product (III). obtain. When contacting, use an inert hydrocarbon solvent (D
₂ ) may be used, or each component may be diluted in advance and used. As the inert hydrocarbon solvent (D ₂ ) to be used, those similar to (D ₁ ) described above can be exemplified. The amount used is 0 to 5,000 ml per 1 mol of the magnesium compound.

There are various methods of contact, for example,
(X ₁ ) is added to a liquefied magnesium compound to precipitate a solid, and the solid is brought into contact with any of (X ₂ ), (B ₁ ), and (T ₁ ). 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, immobilization is precipitated, 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 use amount of each component is within the above-mentioned range, but these components may be used at one time or may be used in several stages. In addition, as described above, when one component has an atom or a group that also characterizes the other component, new use of the other component is not always necessary. For example, when using titanic acid ester when liquefied magnesium compound If (T ₁₎ is, using a halogen-containing titanium compound as a precipitating agent (X ₁₎ (X ₂₎ and (T ₁₎
However, when a halogenating agent is used as the precipitant (X ₁ ), (X ₂ ) is an optional component.

The contact temperature of each component is −40 ° C. to + 180 ° C., preferably −20 ° C. to + 150 ° C., and the contact time is 5 minutes to 8 hours for each step at a reaction pressure of atmospheric pressure to 10 kg / cm ² G, Preferably 1
0 minutes to 6 hours.

The solid product (I) is obtained by the above contact 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 fixed product (I) obtained by the above method is subjected to a polymerization treatment with dimethylstyrene in the presence of the organoaluminum compound (AL ₁ ) to obtain a solid product (II).

The polymerization treatment with dimethylstyrene was carried out by adding 100 ml of an inert hydrocarbon solvent (D ₃ ) to 100 g of the solid product (I).
5,000 ml, 5 g to 5,000 g of an organoaluminum compound (AL ₁ ) were added, and dimethylstyrene was added under the conditions of a reaction temperature of 0 ° C to 90 ° C for 1 minute to 10 hours and a reaction pressure of atmospheric pressure to 10 kg / cm ² G.
Add 0.01 g to 100 kg and polymerize so that the content of the dimethylstyrene polymer in the final titanium catalyst component will be 0.01% to 99% by weight. The content of the dimethylstyrene polymerization pair is 0.
If it is less than 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.

In the polymerization step, 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 usage is from 0 to 5,000 g per 100 g of solid product (I).

Organoaluminum compound used for polymerization (A
L ₁ ) has a general formula of AlR ¹ mR ² _{m ′} X _{3- (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X Represents halogen and m and m'represent any number of 0 <m + m'≤3), and specific examples thereof include trimethylaluminum, triethylaluminum, tri-n-propylaluminum and tri-n. -Butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-
Trialuminylaluminums such as methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, dii
-Dialkylaluminum monohalides such as butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide and diethylaluminum monoiodide; dialkylaluminum hydrides such as diethylaluminum hydride; methylaluminum sesquichloride; ethylaluminum sesquichloride Monoalkylaluminum dihalides such as alkylaluminum sesquihalides, ethylaluminum dichloride, and i-butylaluminum dichloride; and alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum. Can also. These organic aluminums may be used as a mixture of two or more.

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

The dimethylstyrene used in the polymerization treatment is one or more dimethylstyrenes selected from 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene.

Polymerization with dimethylstyrene is performed as described above, and the solid product (II) is obtained by washing with the aforementioned inert hydrocarbon solvent.

Then, the fixed product (II) is reacted with a titanium halide compound (T ₂ ) to obtain a titanium catalyst component containing a dimethylstyrene polymer. The titanium halide compound (T ₂ ) is most preferably titanium tetrachloride.

The reaction between the solid product (II) and the titanium halide compound (T ₂ ) is performed by using the magnesium compound 1 in the solid product (II).
The reaction temperature is 20 ° C. to 200 ° C., the reaction pressure is 5 minutes to 6 hours under the conditions of atmospheric pressure to 10 kg / cm ² G, using 1 mol or more of the titanium halide compound (T ₂ ) per mol. Preferably 10
Allow to react for minutes to 5 hours. It is also possible to carry out the reaction in the presence of an inert hydrocarbon solvent (D ₄ ) and an electron donor (B ₃ ), and specifically, the above-mentioned (D ₁ ) to
The same inert solvent and electron donor as (D ₃ ) and (B ₁ ) are used.

These are used in an amount of 0 to 5,000 ml for (D ₄ ) per 100 g of the solid product (II), and 0 to 2 mol for (B ₃ ) per 1 mol of the magnesium compound in the solid product (II). 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, an α-olefin polymerized titanium catalyst component containing 0.01% to 99% by weight of the dimethylstyrene polymer of the present invention and containing titanium, magnesium, halogen and an electron donor as essential components is obtained.

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

The dimethylstyrene polymer-containing titanium catalyst component is used as a catalyst in combination with organoaluminum (AL ₂ ) and an electron donor (B ₄ ), or as a catalyst preliminarily activated by polymerizing a small amount of α-olefin, Used in the polymerization of α-olefins.

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 described above can be used. Also, electron donor (B ₄ )
As the organic acid ester, an organic silicon compound having an Si—O—C bond such as an alkoxysilane compound or an aryloxysilane compound, an ether, a ketone, an acid anhydride or an amine is preferably used. Specifically, the electron donors (B ₁ ) to (B ₃ ) used in producing the titanium catalyst component described above.
In addition to those exemplified as 2,2,6,6-tetramethylpiperidine, amines with large steric hindrance such as 2,2,5,5-tetramethylpyrrolidine, trimethylmethoxysilane, trimethylethoxysilane, and dimethyldimethoxysilane. ,
Dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyl Triethoxysilane, butyltriethoxysilane, phenyltriethoxysilane,
Examples thereof include organic silicon compounds having a Si—O—C bond such as ethyltri i-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 g to 500 g of an organoaluminum compound (AL ₂ ) and an electron donor ( B ₄₎ is about 0.01g~200g.

The α-olefin used for preactivation includes ethylene, propylene, butene-1, pentene-
Linear olefins such as 1, hexene-1 and heptene-1; and branched monoolefins such as 4-methyl-pentene-1 and 2-methyl-pentene-1.

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

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

A catalyst that combines a titanium catalyst component with an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ) is sufficiently effective for slurry polymerization or bulk polymerization, but in the case of gas phase polymerization, α-olefin is reacted. Those that have been pre-activated by this are desirable. When performing gas phase polymerization subsequent to slurry polymerization or bulk polymerization, even if the initially used catalyst is the former, since the reaction of α-olefin has already been performed during gas phase polymerization, the latter catalyst and The same effect is obtained and an excellent effect is obtained.

The pre-activation is propane, butane, n-pentane, n-
It can be carried out in a hydrocarbon solvent such as hexane, n-heptane, benzene or toluene, can be carried out in a liquefied α-olefin such as liquefied propylene or liquefied butene-1, or can be carried out in gaseous ethylene or propylene. Hydrogen may be allowed to coexist during the conversion.

At the time of preactivation, polymer particles obtained by slurry polymerization, bulk polymerization, or gas phase polymerization may be allowed to coexist. 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 g per 1 g of the titanium catalyst component.
In the range of ~ 5,000g.

The solvent or α-olefin used in the preactivation is
It may be removed during the pre-activation or after completion of the pre-activation by distillation under reduced pressure or by filtration, or the solid product may be removed.
Solvents can also be added to suspend the solvent in an amount not exceeding 80 per gram.

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 the α-olefin, as described above, n-pentane, n-hexane,
Slurry polymerization performed in a hydrocarbon solvent such as n-heptane, n-octane, benzene or toluene, bulk polymerization performed in a liquefied α-olefin monomer such as liquefied propylene or liquefied butene-1, α-olefin such as ethylene or propylene Gas phase polymerization to polymerize in the gas phase, or
There is a method of stepwise combining two or more of the above items. In any case, the polymerization temperature is from room temperature (20 ℃) to 200
° C., the polymerization pressure is in the normal pressure ^{(0kg / cm 2 G) ~50kg} / cm 2 G, is carried out usually about 5 minutes to 20 hours.

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

Further, α-olefins used for the polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 4-methylpentene-1, 2-methylpentene-1 and the like. Branched-chain monoolefins, diolefins such as butadiene, isoprene, chloroprene, etc., and not only homopolymerization of each of these but also in combination with other α-olefins such as 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. It is also possible to carry out block copolymerization by changing the type.

[Action]

The α-olefin polymer obtained by using the titanium catalyst component of the present invention contains a highly stereoregular dimethylstyrene polymer in an extremely dispersed state, so that the dimethylstyrene employee pair nucleates during melt molding. By exhibiting an action, the spherulite size of the α-olefin polymer is reduced,
As a result of promoting crystallization, the transparency and crystallinity of the entire α-olefin polymer are increased.

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

〔The invention's effect〕

The main effect of the present invention is that the titanium catalyst component of the present invention is α
Α-as a transition metal compound catalyst component for olefin polymerization
When used for the polymerization of olefins, it is possible to produce an α-olefin polymer having extremely high productivity and extremely low void generation, and having extremely high transparency and crystallinity.

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

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

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 dimethylstyrene polymer, and is obtained by using the titanium catalyst component. Compared with the obtained α-olefin polymer, it is about 1/4 to 1/2, and has a remarkably high transparency.

Also, the crystallization temperature is increased by about 5 ° C. to 9 ° C. as compared with the case where the dimethylstyrene polymer is not contained, so that the crystallinity is remarkably improved and the flexural modulus is also remarkably increased (Examples 1 to 9). , Comparative Examples 1, 5 to 10).

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

A second effect of the present invention is that an α-olefin polymer having good particle shape and high stereoregularity can be obtained with extremely high polymerization activity. 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 α-olefin polymerization of the present invention is excellent in storage stability and thermal stability. It is extremely important in industry to be able to store for a long time stably regardless of the temperature of the outside temperature. In addition,
The preservation can be carried out in a powder state or in a state of being suspended in an inert hydrocarbon solvent.

Furthermore, the fourth effect of the present invention is that the titanium catalyst component for α-olefin polymerization of the present invention is excellent in abrasion resistance. The titanium catalyst component is not easily crushed at the time of its use, that is, not only in the process of producing the α-olefin polymer but also in the process of producing the catalyst. This means that the formation of the finely divided catalyst is prevented, and thus the formation of the finely divided α-olefin polymer is prevented. As a result, it is very effective in preventing line blockage troubles in the gas phase polymerization process, compressor troubles caused by mixing of the fine powder α-olefin polymer into the circulating gas, and the like.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. The definitions of terms used in Examples and Comparative Examples and 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 haze inside the film excluding the influence 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 of α-olefin polymer powder 150μ thick
After applying liquid paraffin to both surfaces of the film, the haze was measured according to JIS K 7105.

(Unit:%) Crystallization temperature: Measured using a differential scanning calorimeter at a temperature reduction 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 part by weight) were mixed, and the navy blue product was screw screw diameter 40 mm.
Was granulated using an extrusion granulator. Next, a JIS type test piece was prepared from the granulated product using an injection molding machine at a molten resin temperature of 230 ° C and a mold temperature of 50 ° C.
%, Room temperature at 23 ℃ for 72 hours, JIS K720
The flexural modulus was measured according to 3.

(Unit: kgf / cm ² ) Void: α-olefin polymer is granulated in the same manner as in the previous section, and the obtained granule is extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine. 1mm thick with cooling roll at 20 ℃
Created a sheet. 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 were indicated by Δ, and 50 or more were indicated by ×.

Example 1 (1) Production of titanium catalyst component Decane 3 was placed in a stainless steel reactor equipped with a stirrer.
480 g of anhydrous magnesium chloride, 1.7 kg of n-butyl orthotitanate and 1.95 kg of 2-ethyl-1-hexanol
Was mixed and heated at 130 ° C. for 1 hour with stirring to dissolve to form a uniform solution. The homogeneous solution was heated to 70 ° C., 80 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,
It was further heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give solid product (I).

450 g of triethylaluminum and diphenyldimethoxysilane 14 were maintained at 30 ° C.
After suspending in hexane 10 containing 5 g, 3,4-kg of 2,4-dimethylstyrene 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 n-hexane 6 and removing the supernatant liquid by decantation was repeated 4 times, and the solid product (I
I got.

The total amount of the solid product (II) was 1,2-dichloroethane 5
Was mixed with titanium tetrachloride 5 dissolved in, followed by addition of 180 g of diisobutyl phthalate and reaction at 100 ° C. for 2 hours with stirring. Then, the liquid phase portion was removed by decantation at the same temperature, and 1, again. 2-Dichloroethane 5 and titanium tetrachloride 5 were added, 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 has a particle shape close to spherical, and titanium 1.5
% And 2,4-dimethylstyrene polymer 50.0% by weight
Was contained.

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

(3) Polymerization of α-olefin After 20 kg of polypropylene powder of MFR2.0 was put into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer having an internal volume of 80 and substituted with nitrogen, slurry (titanium) was added to the pre-activating catalyst. In addition to the catalyst components, triethylaluminum and diphenyldimethoxysilane were continuously supplied at 0.285 mg atom / hr in terms of titanium atom. In addition, the concentration in the gas phase
Hydrogen was supplied to maintain 0.15% by volume and propylene was supplied to maintain a total pressure of 23 kg / cm ² G, and vapor phase polymerization of propylene was continuously carried out at 70 ° C. for 120 hours. During the polymerization period, the polymer retention level in the polymerization vessel is 60% by volume.
The polymer was continuously extracted from the polymerization vessel at 10 kg / hr so that The extracted polymer was then treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 1 hour.
After being treated for 5 minutes, it was obtained as a product powder.

(4) Thermal stability test The titanium catalyst component obtained in the same manner as in (1) above was stored at 40 ° C for 4 months, and then propylene was polymerized in the same manner as in (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 20 was obtained in a nitrogen atmosphere and in the same manner as in (1) above. 200 g of titanium catalyst component was added. Subsequently, the circulation pump was operated, and the suspension in the reactor was flowed at a flow rate of 10 / min.
After circulating at 25 ° C. for 4 hours, propylene was polymerized in the same manner as in (2) and (3).

Comparative Example 1 (1) The solid product (I) in (1) of Example 1 was
A titanium catalyst component was obtained in the same manner except that the solid product (II) equivalent was obtained without polymerization treatment with 2,4-dimethylstyrene.

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

(3) Propylene was polymerized in the same manner as in Example 1, (3) except that the preactivated catalyst obtained in (2) was used as the preactivated 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) Propylene was polymerized in the same manner as in (5) 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.

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

(2) The reactor used in (2) of Example 1 was charged with n-heptane 20, 100 g of the titanium catalyst component obtained in (1) above, 400 g of diethylaluminum monochloride 400 g, and 120 g of diphenyldimethoxysilane. -T-butylstyrene
155 g was added and reacted at 40 ° C for 2 hours (titanium catalyst component
1.0 g reaction of rt-butylstyrene per 1 g). Then n
-Washed with heptane and then filtered to obtain a solid, further n-heptane 20, diethylaluminum monochloride 400 g,
After adding 55 g of diphenyldimethoxysilane, 280 g of propylene was supplied and reacted at 30 ° C. for 1 hour (1.8 g reaction of propylene per 1 g of titanium catalyst component).

(3) Instead 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 9 hours after the start of polymerization. did not become.

Comparative Example 3 (1) In (1) of Comparative Example 1, before adding diisobutyl phthalate to a uniform solution of anhydrous magnesium chloride, n-butyl orthotitanate, 2-ethyl-1-hexanol and decane, separately. 100 g of titanium catalyst component obtained in the same manner as in (1) of Comparative Example 1 and triethylaluminum 35
g, and 7.5 g of diphenyldimethoxysilane as a catalyst, 4.3 kg of p- added in 100 of n-hexane.
After t-butylstyrene was polymerized at 60 ° C. for 2 hours, washed with methanol and dried to obtain 3 kg of p-t-butylstyrene polymer, which was pulverized for 5 hours in a vibration mill of 550 g. 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 a uniform 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) was used as the titanium catalyst component.

(3) In (3) of Example 1, the total pressure of the preactivated catalyst obtained in (2) above was 23 kg / cm ² G as the preactivated catalyst.
Polymerization of propylene was carried out in the same manner except that the supply was performed so as to maintain the above.

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

Example 4 1.7 kg of aluminum trichloride (anhydrous) and 0.6 kg of magnesium hydroxide were pulverized in a vibrating mill at 250 ° C. for 3 hours to cause a reaction. The reaction occurred with the generation of hydrogen chloride gas. After completion of the heating, the mixture 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 give a solid product (I).

450 g of triethylaluminum and 75 g of methyl p-t-toluate kept at 25 ° C. in total amount of the solid product (I),
After suspending in hexane 10 containing hexane, 3.7 kg of 2,4-dimethylstyrene was added, and the mixture was stirred at the same temperature for 2 minutes.
The polymerization treatment was performed for an hour. 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).
I got

The whole amount of the solid product (II) was 1,2-dichloroethane 10
Diisobutyl phthalate (0.4 kg) was added together with titanium tetrachloride (10) diluted, and the mixture was reacted at 100 ° C. for 2 hours with stirring, and then the liquid phase part was removed by decantation at the same temperature, again 1,2-dichloroethane (10), Titanium tetrachloride 1
After adding 0 and reacting at 100 ° C. for 2 hours with stirring,
The solid portion was collected by hot filtration, washed with purified hexane, and dried to obtain a titanium catalyst component. The titanium content of the titanium catalyst component was 1.84% by weight, and the content of 2,4-dimethylstyrene polymer was 45.9% by weight.

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

Comparative Example 5 A titanium catalyst component was obtained in the same manner as in Example 4, except that the solid product (I) was converted to the equivalent of the solid product (II) without polymerizing with 2,4-dimethylstyrene. Polymerization of propylene was performed.

Example 5 n-Heptane 8 in a stainless steel reactor with stirrer
, 1.0 kg of anhydrous gnesium 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. Next, the homogeneous solution was cooled to 40 ° C. and 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 n-heptane 7 were placed in a stainless steel reactor equipped with a stirrer.
Then, 100 g of diisobutyl phthalate was added, and after 1 hour at 30 ° C., 11.3 kg of silicon tetrachloride and 500 g of titanium tetrachloride were added dropwise over 1 hour. Then at 30 ℃ for 30 minutes, then 90 ℃
For 1 hour. The solid was separated from the solution and washed with n-heptane to give a solid product (I).

2.5 g of the solid product (I) in terms of magnesium atom was treated with 200 g of triethylaluminum kept at 30 ° C.
2.1 kg of 2,5-dimethylstyrene after suspending in n-heptane 5 containing 60 g of diphenyldimethoxysilane and
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 and washed with n-heptane to obtain a polymerized solid product (II).

The total amount of the solid product (II) contains tetra-remote titanium 6
-Mixed with heptane solution 12 and subsequently added 100 g of diheptyl phthalate and reacted at 50 ° C for 2 hours, washed with n-heptane, further added with 150 ml of titanium tetrachloride and washed at 90 ° C to obtain a titanium catalyst. The ingredients are obtained. The titanium catalyst component had a titanium content of 1.76% by weight and a polyallyltrimethylsilane content of 41.2% by weight.

Subsequently, in (2) of Example 1, 150 g of t-butyldimethoxysilane 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 equivalent of the solid product (II) without the 2,5-dimethylstyrene polymerization treatment.
Gas phase polymerization of propylene was performed.

Example 6 In a stainless steel reactor equipped with a stirrer, 2.5 g of n-decane, 480 g of anhydrous magnesium chloride and 1.95 kg of 2-ethyl-1-hexanol were dissolved by heating at 130 ° C. for 2 hours to form a uniform solution. Phthalic anhydride in this solution
111 g was added, and the mixture was further stirred and mixed at 130 ° C., and phthalic anhydride was dissolved in the homogeneous solution. The thus obtained homogeneous solution was cooled to room temperature, and then the whole amount was dropped into titanium tetrachloride 10 kept at -20 ° C over 1 hour. After the dropping, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° 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. The product (I) was obtained.

450 g of triethylaluminum and diphenyldimethoxysilane having the total amount of the solid product (I) kept at 40 ° C.
After suspending in 5 g of n-decane 10, 3.7 kg of 2,4-dimethylstyrene 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 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 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 1.54 wt% titanium and 48.7 wt% 2,4-dimethylstyrene polymer. Subsequently, n-hexane was added to the titanium color component in a stirrer-equipped polymerization vessel equipped with a two-stage turbine blade having an inner volume of 200,
After making 4.0 wt% n-hexane suspension, the suspension was 0.392 mg atom / hr in terms of titanium atom, 8.5 g / hr of triethylaluminum, and 3.0 g / hr of diphenyldimethoxysilane from the same pipe, Further, n-hexane was continuously supplied at 21 kg / hr from another pipe. Furthermore, the total pressure was adjusted so that hydrogen was maintained so that the concentration in the gas phase of the polymerization vessel was kept at 0.25% by volume.
Propylene was supplied so as to maintain 8 kg / cm ² G, and slurry polymerization of propylene was continuously performed 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, and 10 kg / hr of product powder was continuously obtained.

Comparative Example 7 Titanium catalyst component 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 2,4-dimethylstyrene. Was used to carry out slurry polymerization of propylene in the same manner as in Example 6.

Example 7 In place of anhydrous magnesium chloride in (1) of Example 1, 580 g of magnesium ethoxide and 2,4-
3,5-dimethylstyrene 1.8 instead of dimethylstyrene
A titanium catalyst component was obtained in the same manner except that kg was used, and thereafter, vapor phase polymerization of propylene was carried out in the same manner as (2) and (3) of Example 1.

Comparative Example 8 A titanium catalyst component was obtained in the same manner as in Example 7 except that the solid product (I) was replaced with the fixed product (II) without the polymerization treatment with 3,5-dimethylstyrene. Polymerization of propylene was performed.

Example 8 1.2 kg of polytitanate (pentamer) in place of n-butyl orthotitanate in (1) of Example 1
And a titanium catalyst component was obtained in the same manner except that 0.4 kg of 3,4-dimethylstyrene was used instead of 2,4-dimethylstyrene. 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 3,4-dimethylstyrene. Polymerization of propylene was performed.

Example 9 In Example 6, the amount of 2,4-dimethylstyrene used in obtaining the titanium catalyst component was 2.9 kg, and ethylene was further supplied so that the concentration in the gas phase was kept at 0.2% by volume during propylene polymerization. Other than the above, propylene-ethylene copolymerization was performed in the same manner.

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 2,4-dimethylstyrene. Propylene-ethylene copolymerization was performed.

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

[Brief description of the drawings]

FIG. 1 is a flow sheet illustrating the method of the present invention.

Claims (4)

(57) [Claims] (1) A dimethylstyrene polymer is used in an amount of 0.01% by weight to 99% by weight.
% By weight, butyl orthotitanate, polytitanate n
-One or more titanium compounds selected from butyl or titanium tetrachloride, magnesium chloride, a reaction product of magnesium hydroxide and aluminum chloride or one or more magnesium compounds selected from magnesium ethoxide, chlorine (present in the compound Titanium), triethylaluminum and a titanium catalyst component for α-olefin polymerization, which contains an electron donor as essential components. 2. A dimethylstyrene polymer is 2,4-dimethylstyrene polymer, 2,5-dimethylstyrene polymer, 3,4-
The titanium composition according to claim 1, which is one or more dimethylstyrene polymers selected from dimethylstyrene polymers and 3,5-dimethylstyrene polymers. 3. A compound obtained by liquefying one or more compounds selected from magnesium chloride, magnesium hydroxide or magnesium ethoxide, a precipitating agent (only when the titanium compound is not a halogen compound), a halogen compound (titanium compound, precipitation). Contacting one or more titanium compounds (T ₁ ) selected from an electron donor and n-butyl orthotitanate, n-butyl polytitanate or titanium tetrachloride (unless all of the agents are halogen compounds). The solid product (I) thus obtained is polymerized with dimethylstyrene in the presence of triethylaluminum to give a solid product (II).
And reacting the solid product (II) with titanium tetrachloride,
A method for producing a titanium catalyst component for α-olefin polymerization, which comprises 0.01% by weight to 99% by weight of a dimethylstyrene polymer, titanium, magnesium, a halogen and an electron donor as essential components. 4. A patent using one or more kinds of dimethylstyrene selected from 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene as dimethylstyrene. The manufacturing method according to claim 3.