JPH0780952B2 - Titanium catalyst component for producing polyolefin and method for producing the same - Google Patents

Description

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

[Conventional technology and its problems]

A crystalline polyolefin such as crystalline polypropylene is obtained by polymerizing an olefin by a so-called Ziegler-Natta catalyst, which is composed of a transition metal compound of Group IV to VI and an organometallic compound of a metal of Group I to III of the periodic table. It is well known that a polyolefin having high polymerization activity and high stereoregularity has been pursued. Among them, a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor is used as a substance exhibiting a remarkably high polymerization activity while maintaining high stereoregularity. In recent years, vigorous studies have been made on a method for producing a polyolefin by polymerizing an olefin with a catalyst in which these are combined. (For example, JP-A-58-83,006, etc.) The present applicant has already made many proposals in this field, for example, JP-A-61-209,207 and JP-A-62-104,8.
No. 10, JP-A-62-104,811 JP, JP-A-62-104,812
JP-A-62-104,813 and the like disclose a method for obtaining a polyolefin 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 polyolefin is translucent, which may impair the commercial value in the application field, and improvement in transparency has been desired. .

On the other hand, attempts have been made to improve the transparency of polyolefin, 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). There is a method of adding a nucleating agent such as polypropylene to polypropylene, but when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient, and,
When a benzylidene sorbitol derivative is used,
Although some improvement was seen in transparency, there were problems such as strong odor during processing and bleeding of the additive (embossing).

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 continuous polymerization method, particularly a gas phase polymerization method in which olefin polymerization is carried out in a gas phase. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

As a similar technique, a method of polymerizing propylene using the catalyst component obtained by adding a pt-butylstyrene polymer 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 present inventors have earnestly studied a method for solving the problems of the prior art, such as formation of a lump polymer and void generation of a film due to poor dispersion, when producing a polyolefin having improved transparency.

As a result, a titanium catalyst component containing a crystalline allyltoluene polymer and / or a crystalline allylxylene polymer was found by a specific method, and when a catalyst obtained by combining this titanium catalyst component with an organoaluminum compound was used, As described above, it is possible to solve the problems in the production of the polyolefin of the prior art, and to obtain a polyolefin having excellent dispersibility and extremely few voids, which is excellent in transparency and crystallinity. The present invention has been completed by knowing that it has a remarkable effect also on the storage stability at high temperatures of 35 ° C. or higher and on the attrition resistance in the production apparatus during the large-scale production of the titanium catalyst component.

An object of the present invention is to provide a method for producing a titanium catalyst component for producing a polyolefin capable of producing a polyolefin having extremely high transparency and extremely high crystallinity, which is extremely low in void generation with extremely high productivity. .

[Means for Solving the Problems] The present invention has the following configurations.

(1) Crystalline allyltoluene polymer and / or crystalline allylxylene polymer in an amount of 0.01% by weight to 99% by weight, and a liquefied magnesium compound, a depositing agent, a halogen compound, an electron donor and tetravalent titanium Compound (Ti)
The solid product (I) obtained by contacting with is subjected to a polymerization treatment with allyltoluene and / or allylxylene in the presence of an organoaluminum compound to obtain a solid product (II), and the solid product (II) 0.01 to 99% by weight of a crystalline allyltoluene and / or crystalline allylxylene polymer obtained by reacting a titanium halide compound (T ₂ ) with
A titanium catalyst component for producing polyolefin, which contains titanium, magnesium, halogen, and an electron donor as essential components.

(2) The crystalline allyltoluene polymer and / or the crystalline allylxylene polymer is a crystalline o-allyltoluene polymer, a crystalline p-allyltoluene polymer, or a crystalline 2-
Allyl-p-xylene polymer, crystalline 4-allyl-o-
The titanium catalyst component according to item 1, which is one or more crystalline polymers selected from xylene polymers and crystalline 5-allyl-m-xylene polymers.

(3) Liquefied magnesium compound and precipitant, halogen compound, electron donor and tetravalent titanium compound (Ti)
The solid product (I) obtained by contacting with is subjected to a polymerization treatment with allyltoluene and / or allylxylene in the presence of an organoaluminum compound to obtain a solid product (II), and the solid product (II) 0.01 wt% to 99% of a crystalline allyltoluene polymer and / or a crystalline allylxylene polymer obtained by reacting a titanium halide compound (T ₂ ) with
% By weight and contains titanium, magnesium, halogen,
And a method for producing a titanium catalyst component for producing a polyolefin, which comprises an electron donor as an essential component.

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

(5) o-allyltoluene, p-allyltoerene, 2 as allyltoluene and / or allylxylene
-Allyl-p-xylene, 4-allyl-o-xylene,
And the production method according to the above item 3, wherein one or more monomers selected from 5-allyl-m-xylene are used.

The titanium catalyst component for producing a polyolefin of the present invention contains a crystalline allyltoluene polymer and / or a crystalline allylxylene polymer (hereinafter sometimes referred to as a specific allyl polymer), and titanium, magnesium, A titanium catalyst component for producing polyolefin, which contains halogen and an electron donor as essential components, the production method thereof will be described.

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

The magnesium compound to be liquefied may be any as long as it can be in the above-mentioned "liquefied" state, for example, magnesium dihalide, alkoxy magnesium halide, aryloxy magnesium halide, dialkoxy magnesium, diaryloxy. In addition to magnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate, dialkyl magnesium, alkyl magnesium halide and the like, metal magnesium can 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.), a combination of these methods can be used. In addition, it is not possible to apply the above method, for the organomagnesium compound having a C-Mg bond, since it is soluble in ether, dioxane, pyridine, etc., it is used as a solution of these, or by reacting with an organometallic compound, The general formula is
M _p M _q R ³ _r R ⁴ _s (M is aluminum, zinc, boron or beryllium atom, R ₃ and R ₄ are hydrocarbon residues, p, q, r,
When s> O and v are valences of M, there is a relation of r + S = VP + 2q. ) To form a complex compound (JP-A-50-1
39,885), and can be liquefied by dissolving in a hydrocarbon solution.

Furthermore, when metallic magnesium is used, a method of liquefying with an alcohol and an orthotitanate ester (Japanese Patent Laid-Open No. S51-51587, etc.), etc., or by reacting with an alkyl halide in ether, a so-called Grignard reagent is used. It can be liquefied by the method of forming.

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 ⁵ ) ₄ and R ⁶ O-Ti (OR ⁷ ) (OR ⁸ ) _t OR
^{An example} is polytitanate represented by ⁹ . Here, R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms,
t is a number of 2 to 20.

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

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

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

The solid product (I) is obtained by contacting the liquefied magnesium compound with the extruding agent (X ₁ ), halogen compound (X ₂ ), electron donor (B ₁ ) and titanium compound (T ₂ ). .
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 precipitation agents (X ₁ ) used is 0.1 mol to 5 mol per 1 mol of the magnesium compound.
Use 0 mol.

In addition, examples of the halogen compound (X ₂ ) include halogen and compounds having a halogen, and the same halogenating agents as the examples of the precipitating agent can be used. In that case, new use of the halogen compound (X ₂ ) is not necessarily required. The halogen compound (X ₂ ) is used in an amount of 0.1 mol to 50 mol per mol of the magnesium compound.

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

Specifically, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenol, Cresol, xylenol, phenols such as ethylphenol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, ketones such as benzophenone, acetaldehyde, propionaldehyde, aldehydes such as benzaldehyde, formic acid, acetic acid,
Carboxylic acids such as propionic acid, butyric acid and valeric acid, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, octyl acetate, phenyl acetate, propionic acid Aliphatic carboxylic acid esters such as ethyl, methyl benzoate,
Aromatic monocarboxylic acid esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, phenyl anisate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n phthalate -Propyl, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate , Di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate,
Aromatic polyvalent carboxylic acid esters such as dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, di-i-butyl 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; phosphinites such as ethyldiethylphosphinite and ethylbutylphosphinite. Alkoxysilanes such as tetraethoxysilane and tetrabutoxysilane are used, preferably aromatic monocarboxylic acid esters, aromatic polycarboxylic acid esters, alkoxysilanes, and particularly preferably aromatic. Polyvalent 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 ¹⁰ ) _4-u X _u (wherein R ¹⁰ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u represents any 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 are the same as those 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 ₁ ), (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 ℃ to + 180 ℃, preferably -20 ℃
℃ ~ +150 ℃, contact time is atmospheric pressure ~ 10k
g / cm ² G for each step 5 minutes to 8 hours, preferably 10 minutes to
6 hours.

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

Next, the solid product (I) obtained by the above method is sometimes referred to as allyltoluene and / or allylxylene (hereinafter, referred to as a specific allyl monomer) in the presence of the organoaluminum compound (AL ₁ ). ), A solid product (II) is obtained.

The polymerization treatment with the specific allyl monomer 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
The reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 hours, the reaction pressure is atmospheric pressure to 10 kg / cm ² G, and 0.01 g to 100 kg of the specific allyl monomer is added to the final titanium. Polymerization is performed so that the content of the specific allyl polymer in the catalyst component is 0.01% by weight to 99% by weight. When the content of the specific allyl polymer is less than 0.01% by weight, the effect of improving transparency and crystallinity of the polyolefin produced using the titanium catalyst component obtained is insufficient, and when it exceeds 99% by weight. The improvement effect is not remarkable, which is economically disadvantageous.

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

Organoaluminum compound used for polymerization (AL ₁ )
Has a general formula of AlR ¹ _m R ² _{m ′} X _{3- (m + m ′)} (wherein R ¹ , R 2
² represents a hydrocarbon group or an alkoxy group such as an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and m and m'represent any number of 0 <m + m'≤3. ), As a specific example,
Trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2
-Methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and other trialkylaluminums, diethylaluminum monochloride, di-n-propylaluminum monochloride, dii
-Dialkyl aluminum monohalides such as butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide and diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalides, ethyl aluminum dichloride, i-butyl aluminum dichloride, and other monoalkyl aluminum dihalides, and the like. In addition, alkoxyalkyl aluminums such as monoethoxy diethyl aluminum and diethoxy monoethyl aluminum should be used. You can also Two or more kinds of these organoaluminums can be mixed and used.

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

The allyltoluene and / or allylxylene used in the polymerization treatment is selected from o-allyltoluene, p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, 5-allyl-m-xylene. One or more types of monomers.

The solid product (II) is obtained by carrying out the polymerization treatment with the specific allyl monomer 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 specific allyl polymer. Titanium halide compound (T ₂ )
Is the general formula Ti (OR ¹⁰ ) given as an example of the titanium compound (T ₁ ) necessary for the preparation of the solid product (I) described above.
_4-u X _u (wherein R ¹⁰ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u represents 0 <u
It is an arbitrary number of ≦ 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. Remove reactants or by-products.

Thus, the specific allyl polymer of the present invention is added in an amount of 0.01% by weight to 99%
A titanium catalyst component for producing polyolefin, which contains titanium by weight, and contains titanium, magnesium, halogen, and an electron donor as essential components, can be obtained.

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

The specific allyl polymer-containing titanium catalyst component is used as a catalyst in combination with an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ), or a small amount of olefin is further polymerized to preactivate the olefin. Used for polymerization.

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

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

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

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

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

For slurry polymerization or bulk polymerization, a catalyst in which a titanium catalyst component is combined with an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ) is sufficiently effective,
In the case of gas phase polymerization, it is desirable to react with an olefin to preactivate it. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, it is the same as the latter catalyst because the olefin reaction has already been carried out during gas phase polymerization. And an excellent effect is obtained.

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

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

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

A catalyst comprising the titanium catalyst component of the present invention, an organoaluminum compound (AL ₂ ) and an electron donor (B ₄ ) combined as described above, or a catalyst pre-activated with an olefin, is used for the production of a polyolefin. To be As a polymerization method for polymerizing an olefin, as described above,
Slurry polymerization conducted in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene or toluene, liquefied propylene, liquefied butene-
Bulk polymerization carried out in a liquefied olefin monomer such as 1.
There is a gas phase polymerization in which an olefin such as ethylene or propylene is polymerized in a gas phase, or a method of stepwise combining two or more of the above. In any case, the polymerization temperature is room temperature (20 ℃) to 200 ℃, and the polymerization pressure is normal pressure (0kg / cm ² G) to 5
It is usually carried out at 0 kg / cm ² G for about 5 minutes to 20 hours.

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

The olefins used for the polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, and octene-1, 4-methylpentene-1,2-
Branched chain mono-olefins such as methyl-pentene-1, di-olefins such as butadiene, isoprene, chloroprene, etc., and not only homopolymerization of each of these, but also in combination with each other, other olefins, For example, copolymerization can be carried out by combining propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or by combining three components such as propylene, ethylene and butene-1, and by multistage polymerization. Block copolymerization can also be performed by changing the type of olefin to be fed.

[Action]

The polyolefin obtained using the titanium catalyst component of the present invention contains a highly stereoregular specific allyl polymer in an extremely dispersed state, so that the specific allyl polymer exhibits a nucleating action during solvent molding. By demonstrating that the spherulite size of the polyolefin is reduced and crystallization is accelerated,
It enhances the transparency and crystallinity of the entire polyolefin.

Further, since the specific allyl polymer introduced into the polyolefin by using the titanium catalyst component of the present invention is the high 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 when the titanium catalyst component of the present invention is used as a transition metal compound catalyst component for polyolefin production in the polymerization of polyolefin, the generation of voids is extremely low with extremely high productivity, transparency and crystallinity. That is, a polyolefin having extremely high properties can be produced.

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

The first effect of the present invention is that when it is used for olefin polymerization, both transparency and crystallinity of the obtained polyolefin are improved and the number of generated voids is extremely small.

As will be apparent from the examples shown below, the internal haze of the press film of the polyolefin obtained by using the titanium catalyst component of the present invention does not contain a specific allyl polymer, and the polyolefin obtained by using the titanium catalyst component is About 1/4
It is ~ 1/2 and has extremely high transparency.

In addition, the crystallization temperature is increased by about 5 ° C to 9 ° C as compared with the case where the specific allyl polymer is not contained, and the crystallinity is remarkably improved and the flexural modulus is also remarkably increased (Example 1). 9 to Comparative Examples 1, 5 to 10).

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

The second effect of the present invention is an extremely high polymerization activity,
That is, a polyolefin 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 polyolefin can be produced by a continuous polymerization method for a long period of time by a simpler process such as a gas phase polymerization method, which is extremely advantageous in industrial production. Is.

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

Furthermore, a fourth effect of the present invention is that the titanium catalyst component for producing a polyolefin of the present invention has excellent abrasion resistance. The titanium catalyst component is less susceptible to grinding during use, that is, not only during the polyolefin production process but also during the catalyst production process.
This means preventing the formation of finely divided catalyst and thus the formation of finely divided polyolefin. 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 finely divided olefins into the circulating gas.

〔Example〕

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 gram atom of titanium (unit: kg / gram atom) II: Stereoregularity, 20 ° C n-hexane extraction residual amount (unit: wt%) BD: Bulk specific gravity (Unit: g / ml) MFR: Melt Flow Index According to ASTM D-1238 (L). (Unit: g / 10 minutes) Internal haze: The internal haze excluding the effect of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg / cm ² G
Under the conditions described above, a polyolefin powder was formed into a film having a thickness of 150 μ, liquid paraffin was applied to both surfaces of the film, and then the haze was measured according to JIS K 7105. (unit:
%) Crystallization temperature: measured with a differential scanning calorimeter at a temperature decrease rate of 10 ° C./min. (Unit: ° C) Flexural modulus: 100 parts by weight of polyolefin 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 test piece has a humidity of 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: Polyolefin is granulated in the same manner as in the previous section, and the resulting granulated product is extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine, A sheet having a thickness of 1 mm was prepared with a cooling roll. The sheet 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 to measure the number of voids having a diameter of 10 μm or more, 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, 3 l of decane,
480g anhydrous magnesium chloride, 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 while 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 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (I).

450 g of triethylaluminum and 145 g of diphenyldimethoxysilane whose total amount of the solid product (I) was maintained at 30 ° C.
After suspending in 10 l of hexane containing 4-allyl-o-
5.4 kg of xylene was added, and a polymerization treatment was performed 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, subsequently 180 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. The liquid phase portion was removed by decantation at a temperature, 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 titanium catalyst component. 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 4-allyl-o-xylene polymer.

(2) Preparation of pre-activated catalyst After replacing the stainless 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 (1) were obtained. 170 g of titanium catalyst component was added at room temperature. The reactor was maintained at 30 ° C., and 160 Nl of ethylene was fed at the same temperature for 2 hours to cause a reaction (per 1 g of titanium catalyst component, 1.0 g of ethylene was reacted), and then unreacted ethylene was removed.
A preactivated catalyst was obtained.

(3) Polymerization of α-Olefin 20 kg of polypropylene powder of MFR2.0 was charged into a horizontal polymerization vessel of L / D = 3 equipped with a stirrer having an internal volume of 80 liter, which was replaced with nitrogen, and then the pre-activated 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) was added in the same manner as in Example 1 (1).
A titanium catalyst component was obtained in the same manner except that the solid product (II) equivalent was obtained without polymerizing with -allyl-o-xylene.

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

(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 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 diphenylmethoxysilane, propylene 2
80 g was supplied and reacted at 30 ° C. for 1 hour (1.8 g of propylene reacted per 1 g of titanium catalyst component).

(3) In place of the preactivated catalyst slurry in (3) of Example 1, the catalyst slurry obtained in (2) above was further added with triethylaluminum at 1.7 g / hr and diphenyldimethoxysilane at 0.3 g / hr, Polymerization of propylene was carried out in the same manner except that they were supplied from different supply ports. The produced bulk polymer clogged the powder extraction pipe, so the production 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 the homogeneous solution of anhydrous magnesium chloride, n-butyl orthotitanate, 2-ethyl-1-hexanol, and decane in (1) of Comparative Example 1, Separately, 100 g of titanium catalyst component and triethylaluminum obtained in the same manner as in (1) of Comparative Example 1
Using 35 g and 7.5 g of diphenyldimethoxysilane as a catalyst, 4.3 kg of p was added in 100 l of n-hexane.
After polymerizing -t-butylstyrene at 60 ° C for 2 hours, washing with methanol and drying, 385 g of 3 kg of pt-butylstyrene polymer obtained was ground in a vibration mill for 5 hours, and Comparative Example 1 except that it is suspended in a uniform solution of
A titanium catalyst component was obtained in the same manner as in (1).

(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 In (1) of Example 1, the content of crystalline 4-allyl-o-xylene polymer was changed by changing the amount of 4-allyl-o-xylene used in the polymerization treatment. To obtain 0.001 wt%, 4.8 wt% and 28.6 wt% titanium catalyst components, respectively.
After that, propylene was polymerized in the same manner as in (2) and (3) of Example 1.

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

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

The total amount of the solid product (I) was suspended in 10 l of hexane containing 450 g of triethylaluminum and 75 g of methyl p-toluate kept at 25 ° C., and then 5.7 kg of 2-allyl-p-xylene was added and stirred. While performing the polymerization treatment at the same temperature for 2 hours. After the treatment, remove the supernatant and n-hexane
The procedure of adding 6 L and removing the supernatant by decantation was repeated 4 times to obtain a solid product (II) subjected to polymerization treatment.

The total amount of the solid product (II) was diluted with 10 liters of 1,2-dichloroethane together with 10 liters of titanium tetrachloride and diisobutyl phthalate.
After adding 0.4 kg and reacting at 100 ° C for 2 hours with stirring, the liquid phase part was removed by decantation at the same temperature,
After again adding 10 liters of 1,2-dichloroethane and 10 liters of titanium tetrachloride and reacting at 100 ° C for 2 hours while stirring, the solid portion was collected by hot filtration, washed with purified hexane and dried to obtain a titanium catalyst component. Got The titanium content of the titanium catalyst component was 2.7% by weight, and the content of crystalline 2-allyl-p-xylene polymer was 20.0% by weight.

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

Comparative Example 5 In Example 4, the solid product (I) was treated with 2-allyl-p.
-Solid product (II) without polymerisation with xylene
A titanium catalyst component was obtained and propylene was polymerized in the same manner except that a corresponding substance was used.

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
5 g of n-heptane containing 200 g of triethylaluminum and 60 g of diphenyldimethoxysilane kept at 30 ° C.
After being suspended in the above solution, 1.4 kg of 2,5-dimeo-allyltoluene 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 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 reacting at 50 ° C. for 2 hours, the mixture was washed with n-heptane, further 150 ml of titanium tetrachloride was added and washed at 90 ° C. to obtain a titanium catalyst component. The titanium catalyst component had a titanium content of 1.88% by weight and a crystalline o-allyltoluene polymer content of 37.5% by weight.

Subsequently, in (2) of Example 1, 150 g of t-butyltriethoxysilane was used instead of diphenyldimethoxysilane.
Was obtained in the same manner as above except that the total amount of the above titanium catalyst component was used as the titanium catalyst component, and then vapor phase polymerization of propylene was carried out in the same manner as in (3) of Example 1.

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

Example 6 n-decane was added in a stainless steel reactor equipped with a stirrer.
2.5 l, anhydrous magnesium chloride 480 g and 2-ethyl-1
-Hexanol (1.95 kg) is heated at 130 ° C for 2 hours to dissolve it into a uniform solution, and then 111 g of phthalic anhydride is added to this solution.
Was added, and the mixture was further stirred and mixed at 130 ° C. to dissolve phthalic anhydride 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 4-allyl-o
-4.8 kg of xylene was added, and a polymerization treatment was performed 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 l of titanium tetrachloride, 350 g of diisobutyl phthalate was subsequently added, and the mixture was reacted at 110 ° C. for 2 hours while stirring, and then decanted at the same temperature to form a liquid phase. After removing the parts, 1,000 ml of titanium tetrachloride was added again, and the mixture was heated at 110 ° C. for 2 hours for heating reaction.

After completion of the reaction, the liquid phase part was removed by decantation at the same temperature, the solid was washed with n-decane and n-hexane at 80 ° C, and dried to obtain a titanium catalyst component. The titanium catalyst component had 1.82% by weight titanium and 39.4% by weight crystalline 4-allyl-o-xylene 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 internal 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 of triethylaluminum and 3.0 g / hr of diphenyldimethoxysilane from the same pipe or from another pipe
-Hexane was continuously fed at 21 kg / hr. Furthermore, hydrogen is supplied so that the concentration in the gas phase of the polymerization vessel is maintained at 0.25% by volume, and propylene is supplied so that the total pressure is maintained at 8 kg / cm ² G, and slurry polymerization of propylene is performed at 70 ° C. for 120 hours. ,
It went continuously. During the polymerization period, the slurry was continuously withdrawn from the polymerization vessel into a flash tank having an internal volume of 50 l so that the retained level of the slurry in the polymerization vessel was 75% by volume.
The pressure is reduced in the flash tank to remove unreacted propylene, while methanol is supplied at 1 kg / hr at 70 ° C.
Was contact-treated. Subsequently, the slurry was separated from the solvent by a centrifuge and then dried by a drier to continuously obtain a product powder at 10 kg / hr.

Comparative Example 7 In Example 6, the solid product (I) was converted to the solid product (II) without polymerization treatment with 4-allyl-o-xylene.
Slurry polymerization of propylene was carried out in the same manner as in Example 6 except that the titanium catalyst component obtained in the same manner as above was used.

Example 7 In (1) of Example 1, 580 g of magnesium ethoxide was used instead of anhydrous magnesium chloride, and 5-allyl-m-xylene was used instead of 4-allyl-o-xylene.
A titanium catalyst component was obtained in the same manner except that 2.9 kg was used, and thereafter, vapor phase polymerization of propylene was carried out in the same manner as in (2) and (3) of Example 1.

Comparative Example 8 In Example 7, the solid product (I) was converted to the solid product (II) without the polymerization treatment with 5-allyl-m-xylene.
A titanium catalyst component was obtained and propylene was polymerized in the same manner except that a corresponding substance was used.

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 0.85 kg of p-allyltoluene was used instead of 4-allyl-o-xylene. Then, using the titanium catalyst component 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-allyltoluene. Was polymerized.

Example 9 In Example 6, the amount of 4-allyl-o-xylene used in obtaining the titanium catalyst component was 4.4 kg, and ethylene was further supplied so that the concentration in the gas phase was 0.2% by volume during propylene polymerization. Other than the above, propylene-ethylene copolymerization was performed in the same manner.

Comparative Example 10 In Example 9, the solid product (I) was converted to the solid product (II) without the polymerization treatment with 4-allyl-o-xylene.
A titanium catalyst component was obtained and propylene-ethylene copolymerization was carried out in the same manner except that a corresponding substance was used.

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 manufacturing process diagram illustrating a method of the present invention.

Claims (5)

[Claims] 1. A crystalline allyltoluene polymer and / or a crystalline allylxylene polymer in an amount of 0.01% by weight to 99% by weight.
Included and liquefied magnesium compound and precipitation agent,
The solid product (I) obtained by contacting a halogen compound, an electron donor and a tetravalent titanium compound (Ti) is polymerized with allyltoluene and / or allylxylene in the presence of an organoaluminum compound to give a solid product. A crystalline allyltoluene polymer and / or a crystalline allylxylene polymer obtained by reacting the solid product (II) with a titanium halide compound (T ₂ ) is added to 0.01
% To 99% by weight and contains titanium, magnesium,
A titanium catalyst component for producing polyolefin, which contains halogen and an electron donor as essential components. 2. A crystalline allyltoluene polymer and / or a crystalline allylxylene polymer is a crystalline o-allyltoluene polymer, a crystalline p-allyltoluene polymer, or a crystalline 2-allyl-p-xylene polymer. Combined, crystalline 4-allyl-o-xylene polymer, and crystalline 5-allyl-m-
The titanium catalyst component according to claim 1, which is one or more crystalline polymers selected from xylene polymers. 3. A liquefied magnesium compound and a precipitation agent,
The solid product (I) obtained by contacting a halogen compound, an electron donor and a tetravalent titanium compound (Ti) is polymerized with allyltoluene and / or allylxylene in the presence of an organoaluminum compound to give a solid product. A crystalline allyltoluene polymer and / or a crystalline allylxylene polymer obtained by reacting the solid product (II) with a titanium halide compound (T ₂ ) is added to 0.01
% To 99% by weight and contains titanium, magnesium,
A method for producing a titanium catalyst component for producing a polyolefin, which comprises halogen and an electron donor as essential components. 4. An organoaluminum compound having the general formula
AlR ¹ _m R ² _{m ′} X _{3 − (m + m ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; m,
m ′ represents an arbitrary number of 0 <m + m ′ ≦ 3. The manufacturing method of Claim 3 which uses the organoaluminum compound represented by these. 5. The allyltoluene and / or allylxylene is selected from o-allyltoluene, p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, and 5-allyl-m-xylene. The method according to claim 3, wherein one or more kinds of the prepared monomers are used.