JP2790870B2 - Method for producing catalyst component for olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a process for producing a catalyst component for olefin polymerization, which is capable of obtaining a propylene polymer having excellent transparency and good properties in a high yield. .

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION There have already been many proposals for a method for producing a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components. It is also known that a polymer having high stereoregularity can be produced in a high yield by using it in the polymerization of α-olefin of several or more.

When a propylene-based polymer is produced using the olefin polymerization catalyst component comprising the solid titanium catalyst component and the organoaluminum compound catalyst component as described above, 3-methyl-1-butene is added to the olefin polymerization catalyst component. It has been known that a propylene-based polymer having excellent transparency can be obtained by pre-polymerizing the polymer. By pre-polymerizing 3-methyl-1-butene to the olefin polymerization catalyst component, poly-3-methyl-1-butene becomes a polymer nucleating agent in the propylene-based polymer and reduces the spherulite size of polypropylene. It is presumed that the fineness is reduced and the transparency of the resulting propylene-based polymer is improved.

However, the catalyst component for olefin polymerization described above has 3
When propylene or propylene and another α-olefin are fully polymerized after pre-polymerization of -methyl-1-butene, the resulting propylene-based polymer particles may be partially destroyed, and a finely powdered polymer is formed. There was a problem of doing it. In addition, the propylene-based polymer obtained as described above has a problem that its apparent bulk density is small.

The present inventors have conducted intensive studies to solve the above problems, and found that [A] reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor. Magnesium, titanium,
Using a solid titanium catalyst component containing a halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst component formed from the electron donor, Methyl-1
-Prepolymerization of butene and then prepolymerization of a linear α-olefin having 2 to 5 carbon atoms, or a linear α-olefin having 2 to 5 carbon atoms using the catalyst component for olefin polymerization. Is pre-polymerized, and then propylene or propylene and another α-olefin are (co) polymerized using an olefin polymerization catalyst component obtained by pre-polymerizing 3-methyl-1-butene. It has been found that a propylene-based polymer having excellent and good particle properties can be obtained, and the present invention has been completed.

An object of the present invention is to solve the problems associated with the prior art as described above, and it is possible to obtain a propylene-based polymer having excellent transparency and good properties in high yield. It is an object of the present invention to provide a method for producing an olefin polymer catalyst component as possible.

SUMMARY OF THE INVENTION The method for producing an olefin polymerization catalyst component according to the present invention comprises: [A] a liquid magnesium compound having no reducing property;
A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components obtained by reacting a liquid titanium compound with an electron donor, [B] an organoaluminum compound catalyst component and If necessary, using [C] an olefin polymerization catalyst component [X] formed from an electron donor, 0.1 g / g of the solid portion in the olefin polymerization catalyst component.
1 to 300 g of a linear α-olefin having 2 to 5 carbon atoms is prepolymerized, and then 0.1 g / g of the solid portion in the catalyst component.
It is characterized in that 1 to 100 g of 3-methyl-1-butene is prepolymerized.

In addition, the method for producing the olefin polymerization catalyst component [Y] according to the present invention uses the olefin polymerization catalyst component [X] as described above, and uses 0.1 to 1 to 1 g per 1 g of a solid portion in the catalyst component.
00 g of 3-methyl-1-butene is prepolymerized to obtain 0.1 to 300 g of carbon atoms having 2 to 5 carbon atoms per 1 g of solid portion in the catalyst component.
Is characterized by pre-polymerizing a linear α-olefin.

In the olefin polymerization catalyst component [Y] obtained according to the present invention, 3-methyl-1-butene and C2-C2 are used.
5 is prepolymerized in the presence of the catalyst component [X] to form a block copolymer. Therefore, the propylene polymer produced using the catalyst component [Y] Has excellent transparency and good properties, and also has a large apparent bulk density.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing the olefin polymerization catalyst component [Y] according to the present invention will be specifically described.

In the present invention, the term polymerization may be used in a sense that encompasses not only homopolymerization but also copolymerization,
In addition, the term polymer is sometimes used to mean not only a homopolymer but also a copolymer.

Olefin polymerization catalyst component [X] used when forming olefin polymerization catalyst component [Y] according to the present invention.
Is formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and, if necessary, an electron donor [C].

FIG. 1 shows an example of a flowchart of a method for preparing the olefin polymerization catalyst component [Y] according to the present invention.

The solid titanium catalyst component [A] used in the present invention includes:
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component [A] includes, for example, Ti (OR)
_g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On Monohalogenated trialkoxy titanium such as -C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H) _{9) 4 Ti (Oiso-C} 4 H 9) such as ₄ Ti (O @ 2- _{ethylhexyl) 4} tetraalkoxy titanium, and the like.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium,
Diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, decyl butyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl Butyl magnesium, butyl magnesium halide and the like can be mentioned. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyoxymagne such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, the magnesium compound, in addition to the magnesium compound having a reducing property and the magnesium compound having no reducing property, a complex compound of the magnesium compound and another metal, a double compound or another metal compound. May be used. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

In the present invention, as the electron donor used for preparing the solid titanium catalyst component [A], preferably a polyvalent carboxylic acid ester is used, and specifically, a compound having a skeleton represented by the following formula is used. Can be

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , and R ⁶ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ represent a hydrogen atom Represents a substituted or unsubstituted hydrocarbon group. Preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include N,
Examples include substituted hydrocarbon groups containing a different atom such as O and S, for example, -C-O-C-, -COOR, -COOH, -OH,
Substituted hydrocarbon groups having a structure such as —SO ₃ H, —C—N—C—, and —NH ₂ .

Among these, a diester in which at least one of R ¹ and R ² is derived from a dicarboxylic acid having an alkyl group having 2 or more carbon atoms is preferable.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethylmaleate, monooctylmaleate, diisooctylmaleate, diisobutylmaleate, butylmaleic acid Diisobutyl, diethyl butyl maleate, β
-Aliphatic polycarboxylates such as diisopropyl methyl glutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, dimethyl citrate, 1,2-cyclohexane carboxylate Aliphatic polycarboxylates such as diethyl phosphate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, phthalic acid Diethyl, ethyl isobutyl phthalate, mono-n-butyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobuty phthalate Phthalate, di n- heptyl,
Di-2-ethylhexyl phthalate, didecyl phthalate,
Aromatic polycarboxylic acid esters such as benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic poly such as 3,4-furandicarboxylic acid Esters derived from carboxylic acids can be mentioned.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, and n-sebacate.
Octyl, di-2-ethylhexyl sebacate and the like,
Esters derived from long chain dicarboxylic acids can be mentioned.

Among these polycarboxylic acid esters, compounds having a skeleton represented by the aforementioned general formula are preferred, and more preferably phthalic acid, maleic acid, substituted malonic acid, and the like, and alcohols having 2 or more carbon atoms. Esters are preferred, and diesters obtained by reacting phthalic acid with alcohols having 2 or more carbon atoms are particularly preferred.

As these polycarboxylic acid esters, it is not always necessary to use the above-mentioned polycarboxylic acid esters as starting materials, and these polycarboxylic acid esters are used during the preparation of the solid titanium catalyst component [A]. Using a derivable compound, a solid titanium catalyst component [A]
May be formed at the stage of preparing the polycarboxylic acid.

In the present invention, examples of the electron donor other than the polyvalent carboxylic acid that can be used when preparing the solid titanium-based catalyst [A] include alcohols, amines, amides, and ethers described below. , Ketones, nitriles,
Phosphines, stippines, arsils, phosphoramides, esters, thioethers, thioesters,
Organosilicon compounds such as acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and groups I to IV of the periodic table
Examples include amides and salts of metals belonging to the group.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with an electron donor and a titanium compound. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component [A] will be briefly described below with several examples.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and / or a reaction assistant such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) magnesium compound and alkoxytitanium and / or
Or a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether is reacted with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound. A method in which an electron donor represented by such a phthalic acid diester coexists.

Among the methods for preparing the solid titanium catalyst component [A] described in the above (1) to (9), a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound When used, a method using a halogenated hydrocarbon is preferred.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. In an amount of 5 moles, preferably 0.05-2 moles, the titanium compound is about 0.01-500
It is preferably used in an amount of 0.05 to 300 moles.

The solid titanium catalyst component [A] thus obtained
Contains magnesium, titanium, halogen and an electron donor as essential components.

In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100.
Wherein the electron donor / titanium (molar ratio) is about 0.1 to 1
0, preferably about 0.2 to about 6, and magnesium / titanium (atomic ratio) of about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g.
Or more, preferably about 60~1000m ² / g, more preferably about 10
It is 0 to 800 m ² / g. The solid titanium catalyst component [A] does not substantially change its composition by washing with hexane since the above components are combined to form a catalyst component.

Such a solid titanium catalyst component [A] can be used alone, but also includes, for example, a silicon compound,
It can be used after being diluted with an inorganic compound or an organic compound such as an aluminum compound or polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

For a method of preparing such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51
No. 64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596, No. 52-1
No. 47688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43
No. 094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 61-21109, No. 61-37802, No. 61
-37803, and the like.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms, preferably 1 to X is a hydrocarbon group containing four, and may be the same or different from each other, and X represents a halogen atom;
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number of q <3, moreover organic aluminum compound represented by a is) m + n + p + q = 3, a (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, K, R ¹ Are the same as those described above), and a complex alkylated product of a Group 1 metal and aluminum.

As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m ≦ 3), a general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above; X is a halogen, m is preferably 0 <m <3); and a general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above; m is preferably 2 ≦ m <3); and a general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² is the same as above, X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

As the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, partially alkoxylated alkyl aluminum having a planar composition represented by R ¹ _2.5 Al (OR ² ) _{0.5 and the} like; diethyl aluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride and diethylaluminum bromide; ethylaluminum chloride Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkyl aluminum hydrides such as hydride and dibutyl aluminum hydride; other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride and alkyl aluminum dihydride such as propyl aluminum dihydride; ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, ethyl Alcohol such as aluminum ethoxy bromide Shi reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , Methyl aluminoxane and the like can be mentioned.

Examples of the compound belonging to (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more aluminum compounds described above are bonded.

In the present invention, when producing the olefin polymerization catalyst component [X], an electron donor [C] can be used as necessary. Examples of such an electron donor [C] include alcohols and phenol. , Ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, and ammonia-containing electron donors such as amines, nitriles, and isocyanates Alternatively, the above-described polycarboxylic acid esters and the like can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol,
C1-18 alcohols such as dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propyl Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, nonylphenol, cumylphenol and naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone,
C3-15 ketones such as benzoquinone; C2-15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate;
Methyl acetate, ethyl acetate, vinyl acetate, propyl acetate,
Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl triylate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, phthalate Carbon number 2 such as diisobutyl acid, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
An organic acid ester having a carbon number of 2 to 15, such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether;
C2-C20 ethers such as amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine Amines such as aniline, pyridine, picoline and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [Ia] can also be used.

_{R n Si (OR ') 4} -n ... [I a] [ wherein, R and R' is a hydrocarbon group, 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula [Ia] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t- Butylmethyldimethoxysilane, t
-Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n -Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-amino Propyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxy Silane, ethyl silicate, butyl silicate, trimethylphenoxy silane, methyl triaryloxy (allyloxy) silane, vinyl tris (β-methoxyethoxy silane), Sulfonyl triacetoxy silane, dimethyl tetraethoxy disiloxane is used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Preferred are silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [IIa] can be used.

SiR ¹ R ² _m (OR ³ ) _3-m ... [IIa] wherein R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group and cyclopentyl having an alkyl group A group selected from the group consisting of groups, R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the above formula [IIa], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and as R ¹ , other than a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl And a cyclopentyl group having an alkyl group such as a 2,3-dimethylcyclopentyl group.

In the formula [IIa], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, an alkyl group such as hexyl, or cyclopentyl group having an exemplified cyclopentyl group and an alkyl group as R ¹ can be exemplified similarly.

Further, in the formula [IIa], R ³ is a hydrocarbon group,
As R ³ , for example, an alkyl group, a cycloalkyl group,
And hydrocarbon groups such as aryl groups and aralkyl groups.

Among these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxy Silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldi Chill silane, mono-alkoxysilanes such as cyclopentyl dimethylethoxysilane, and the like.

As the electron donor [C], the above-mentioned organic carboxylic acid esters and organic silicon compounds are preferable, and the organic silicon compounds are particularly preferable.

Olefin polymerization catalyst component [X] used when forming olefin polymerization catalyst component [Y] according to the present invention.
Is formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and, if necessary, the electron donor [C]. First, a linear α-olefin having 2 to 5 carbon atoms is prepolymerized, and then 3-methyl-1-butene is prepolymerized using the catalyst component [X].

As the linear α-olefin having 2 to 5 carbon atoms to be prepolymerized, specifically, ethylene, propylene, n-
Butene-1 and n-pentene-1. These α-olefins may be used alone or in combination.

In the present invention, the olefin polymerization catalyst component [Y]
In the preparation of the above, together with 3-methyl-1-butene, a linear α-olefin is used as described above, so that polymer particles having a small amount of fine powder and a high bulk specific gravity can be obtained.

In the present invention, among the above-mentioned α-olefins, particularly when ethylene is used, a film having excellent blocking resistance can be obtained from an olefin polymer obtained using the obtained olefin polymerization catalyst component [Y]. Can be provided.

In the prepolymerization as described above, the number of carbon atoms is 2-5.
The linear α-olefin is 0.1 to 300 g, preferably 1 to 100, preferably 1 to 100, per 1 g of the solid portion in the olefin polymerization catalyst component.
Particularly preferably, prepolymerization is carried out in an amount of 1 to 50 g, and 3-methyl-1-butene is used in an amount of 0.1 to 100 g, preferably 1 to 50 g, particularly preferably 2 to 20 g per 1 g of a solid portion in the olefin polymerization catalyst component. It is desirable to prepolymerize in an amount.

In the present invention, 3-methyl-1-butene is preliminarily polymerized using the above-mentioned catalyst component for olefin polymerization [X], and then a linear α-olefin having 2 to 5 carbon atoms is preliminarily polymerized. It may be polymerized. At this time, 3-methyl-1
-Butene is a solid component in the olefin polymerization catalyst component.
0.1 to 100 g per g, preferably 1 to 50 g, particularly preferably 2 g
Is prepolymerized in an amount of from 20 to 20 g, and the linear α-olefin having 2 to 5 carbon atoms is 0.1 to 300 g, preferably 1 to 100 g, particularly preferably 1 to 100 g per 1 g of a solid portion in the olefin polymerization catalyst component. It is desirable to prepolymerize in an amount of 50 g.

In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is generally about 0.01 to 200 mmol, preferably about 0.1 to 200 mmol, in terms of titanium atom, per inert hydrocarbon medium described later.
It is desirable to set the range to 100 mmol, particularly preferably 1 to 50 mmol.

The amount of the organoaluminum catalyst component [B] is 1 g of the solid portion.
The amount may be 0.1 to 500 g, preferably 0.3 to 300 g, per 1 mol of titanium atom in the solid titanium catalyst component [A], and is usually about 0.1 to 500 mol, preferably about 1 to 500 mol. Desirably, it is in an amount of 100100 mol.

The electron donor [C] is used as needed, and is used in an amount of 0.1 mol per mol of titanium atom in the solid titanium catalyst component [A].
-100 mol, preferably 1-50 mol, particularly preferably 1
It is preferably used in an amount of up to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Further, it is also possible to use the monomer itself as a solvent or to carry out prepolymerization in a state substantially free of a solvent.

The temperature at the time of the prepolymerization may be a temperature at which the produced prepolymer is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about -20 to + 8 ° C.
The temperature is desirably in the range of 0 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5 to 10 dl / g.

The prepolymerization can be performed in a batch system or a continuous system. Further, for example, prepolymerization of 3-methyl-1-butene is carried out in a batch system, and then linear α
-There may be a combined system in which prepolymerization of the olefin is carried out continuously.

Thus, a pre-polymerization of a linear α-olefin having 2 to 5 carbon atoms and then 3-methyl-1-butene using the catalyst component for olefin polymerization as described above, or 3-methyl-1 -Butene followed by 2 to 5 carbon atoms
Is pre-polymerized, the catalyst component for olefin polymerization contains a linear α-olefin having 2 to 5 carbon atoms.
A block copolymer of olefin and 3-methyl-1-butene is prepolymerized.

Preliminary polymerization is performed on the olefin polymerization catalyst component [X] as described above, and the obtained olefin polymerization catalyst component [Y] or [I], the organoaluminum catalyst component [II], and if necessary, The main polymerization of the olefin is carried out in the presence of an olefin polymerization catalyst formed from the electron donor [III].

In the main polymerization of the olefin, the same organic aluminum component [II] as the organic aluminum [B] used in producing the olefin polymerization catalyst component of the present invention can be used. In the main polymerization of the olefin, the same electron donor [C] used in producing the olefin polymerization catalyst component [Y] of the present invention should be used as the electron donor [III]. Can be. In addition,
The organoaluminum component and the electron donor used in the main polymerization of the olefin need not necessarily be the same as the electron donor used in preparing the olefin polymerization catalyst component [Y] of the present invention.

Examples of the olefin that can be used in the main polymerization include olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, and 1-octene. In the polymerization method of the present invention, these olefins can be used alone or in combination. Of these olefins, it is preferable to carry out homopolymerization using propylene or 1-butene, or to carry out copolymerization using a mixed olefin containing propylene or 1-butene as a main component. When using such a mixed olefin, the content of propylene or 1-butene as a main component is usually 50 mol% or more,
It is preferably at least 70 mol%. In addition,
When copolymerization is performed using a mixed olefin, ethylene can be used as a comonomer.

When performing homopolymerization or copolymerization of these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used as a polymerization raw material.

In the polymerization method of the present invention, the main polymerization of the olefin,
Usually, the reaction is performed in a gas phase or a liquid phase.

When the main polymerization takes a reaction mode of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, and an olefin liquid at the reaction temperature can be used.

In the polymerization method of the present invention, the pre-polymerized olefin polymerization catalyst component [Y] or [I] is usually about 0.001 to 0.5 mmol, preferably about 0.005 to 0.5 mmol, in terms of Ti atom per polymerization volume. Used in an amount of 0.1 mmol. The organoaluminum compound catalyst component [II]
Titanium atom in olefin polymerization catalyst component in polymerization system 1
The metal atom in the organoaluminum compound catalyst component is used in an amount of usually about 1 to 2000 mol, preferably about 5 to 500 mol, per mol. Further, the electron donor [III] is usually used in an amount of about 0.001 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol, per 1 mol of metal atom in the organoaluminum compound catalyst component [II]. It is used in such an amount that

If hydrogen is used during the main polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. Also in this case, in the polymerization method of the present invention, the stereoregularity index of the produced polymer is reduced,
There is no reduction in catalytic activity.

In the present invention, the polymerization temperature of the olefin is usually about
At 20-200 ° C, preferably about 50-100 ° C, the pressure is usually
The pressure is set at normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . In the polymerization method of the present invention, the polymerization is a batch type,
It can be carried out by any of a semi-continuous method and a continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer. Poly 3 in the olefin polymer
The content of -methyl-1-butene is usually 1 to 1000 ppm, preferably 10 to 1000 ppm.

As described above, using a catalyst component [I] for olefin polymerization in which a block copolymer of 3-methyl-1-butene and a linear α-olefin having 2 to 5 carbon atoms is prepolymerized, Polymerization of propylene or propylene and other α-
By copolymerizing with an olefin, it is possible to obtain a propylene-based polymer having excellent transparency and good properties and a large apparent bulk density.

That is, when propylene polymerization or copolymerization of propylene and another α-olefin is carried out using the olefin polymerization catalyst component [I] produced according to the present invention, the resulting propylene-based polymer contains Since a block copolymer of -1-butene and a linear α-olefin having 2 to 5 carbon atoms is present as a polymer nucleating agent, the spherulite size of the propylene-based polymer is reduced, and transparency is improved. An excellent propylene polymer is obtained. Further, a propylene-based catalyst obtained by using an olefin polymerization catalyst component [I] in which a block copolymer of 3-methyl-1-butene and a linear α-olefin having 2 to 5 carbon atoms is preliminarily polymerized. As compared with a propylene-based polymer obtained using a catalyst component for olefin polymerization in which only 3-methyl-1-butene is prepolymerized, the obtained polymer particles are less likely to be broken, and Polymer production can be suppressed, and the apparent bulk density of the obtained propylene-based polymer is high.

Further, in the present invention, the yield of the polymer having stereoregularity per unit amount of the catalyst component for olefin polymerization is high, so that the catalyst residue, particularly the halogen content, in the polymer can be relatively reduced. Therefore, the operation of removing the catalyst in the polymer can be omitted, and rusting of the mold can be effectively prevented when the formed olefin polymer is used to form a molded article.

Effects of the Invention The catalyst component for olefin polymerization according to the present invention includes a solid titanium catalyst component [A] obtained by the above-described specific method and a specific organoaluminum compound catalyst component [B].
And, if necessary, a block copolymer of 3-methyl-1-butene and a linear α-olefin having 2 to 5 carbon atoms which is formed from an electron donor [C] and is prepolymerized. Therefore, when olefin is polymerized using this catalyst, a propylene-based polymer having excellent transparency, good particle properties, and high apparent bulk density can be produced in high yield. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of solid titanium catalyst component [A]] 7.14 kg of anhydrous magnesium chloride, 37.5 and 2 of decane
-Ethylhexyl alcohol 35.1 was heated and reacted at 140 ° C for 4 hours to obtain a homogeneous solution. Thereafter, 1.67 kg of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above-mentioned homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, the whole solution was dropped into titanium tetrachloride 200 kept at -20 ° C over 3 hours. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., 5.03 of diisobutyl phthalate was added.

Stir at the above temperature for another 2 hours. After the completion of the reaction for 2 hours, a solid portion was collected by filtration under hot conditions, and the solid portion was collected for 275 hours.
Was re-suspended in TiCl ₄ and heated again at 110 ° C. for 2 hours.

After the completion of the reaction, a solid portion was collected again by hot filtration and washed with hexane. This washing was performed until no titanium compound was detected in the washing solution.

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of the catalyst was collected and dried. Analysis of the dried product showed that the composition of the solid titanium catalyst component [A] obtained as described above was 2.4% by weight of titanium, 59% by weight of chlorine, 18% by weight of magnesium and 11.6% by weight of diisobutyl phthalate. Was.

[Preliminary polymerization] After adding 100 mol of purified hexane, 3 mol of triethylaluminum and 1 mol of the titanium catalyst component [A] in terms of titanium atom to a reactor purged with nitrogen, the temperature of the suspension was raised to 15 to 20 ° C. Propylene was supplied over 1.5 hours at a rate of 2130 Nl / hour with stirring. After the supply of propylene was completed, the reactor was closed, and polymerization of the remaining propylene was carried out for 30 minutes. Then, 7 mol of triethylaluminum, 5 mol of trimethylmethoxysilane and 5.9 kg of 3-methyl-1-butene were added, and the mixture was added at 20 ° C. The mixture was stirred and mixed for 3 hours to carry out prepolymerization of 3-methyl-1-butene. After the completion of the prepolymerization, it was sufficiently washed with purified hexane. As a result of the analysis, the prepolymerization amount of propylene was 2.8 g / g catalyst solid part, and the prepolymerization amount of 3-methyl-1-butene was 2.4 g / g catalyst solid part.

[Polymerization] Using a polymerization vessel having an internal volume of 250, homopolymerization of propylene was continuously performed. The polymerization pressure was controlled at 8 kg / cm ² G, and the polymerization temperature was controlled at 70 ° C. The catalyst component is triethyl aluminum
18 mmol / h, dicyclohexyldimethoxysilane
1.8 mmol / hr, a propylene and 3-methyl-1-butene prepolymerization catalyst of the titanium catalyst component [A] were continuously supplied based on a rate of 0.24 mmol / hr in terms of titanium atoms. The resulting polypropylene was discharged continuously.

The production rate of the obtained polypropylene is about 10 kg on average
/ H. Poly 3-methyl- in polypropylene
The content of 1-butene was 140 ppm by weight.

<Production method of biaxially stretched film> 0.1 parts by weight of calcium stearate as a stabilizer and 100 parts by weight of polypropylene containing the 3-methyl-1-butene polymer obtained as described above, and BHT (2,6- 0.1 parts by weight of di-tert-butylhydroxytoluene), Irganox 1010 (an antioxidant manufactured by Ciba-Geigy, tetrakis [methylene-3 (3 ', 5'-di-tert-butylhydroxyphenyl) propionate] methane).
Add 1 part by weight, mix with Henschel mixer, then 65mm
The mixture was granulated into pellets at a kneading temperature of 220 ° C. using a φ extruder.

Next, the obtained pellets were treated with a 90 mmφ sheet extruder for 28 hours.
The sheet was extruded at 0 ° C. and formed into a 1.5 mm thick sheet with a cooling roll at 30 ° C. Next, the obtained sheet is stretched 5 times at a stretching temperature of 145 ° C. in a longitudinal direction with a tenter-type sequential biaxial stretching apparatus,
Subsequently, the film was stretched 10 times in the transverse direction in an enter temperature of 170 ° C. to obtain a biaxially stretched film having a thickness of about 30 μm.

<Evaluation method of film> 1) Visual evaluation of transparency Transparency when five 30 μm thick films were stacked and the light of a fluorescent lamp was viewed through the film was visually evaluated in five steps (5-
(Good, 1-bad) Evaluation was made.

2) Dispersion transmitted light intensity (LSI) It was measured by an LSI tester manufactured by Toyo Seiki Co., Ltd.

3) Haze Measured according to ASTM D 1003.

4) Diameter of spherulite The diameter of spherulite in the cross section of the raw sheet before biaxial stretching was measured by a stereoscopic microscope (× 100).

The smaller the spherulite size of the raw sheet, the better the transparency of the biaxially stretched film tends to be. Therefore, it was used as a scale for obtaining a film with good transparency.

 Table 1 shows the results.

Example 2 [Preliminary polymerization] Purified hexane 100, triethylaluminum 10 mol, trimethylmethoxysilane 10 were placed in a reactor purged with nitrogen.
Moles of the titanium catalyst component [A] is 1 in terms of titanium atoms.
After addition of 10 kg of mol and 3-methyl-1-butene,
The suspension was maintained at 20 ° C. for 3 hours with stirring,
Preliminary polymerization of methyl-1-butene was performed. As a result of the analysis, the prepolymerized amount of 3-methyl-1-butene was 3.9 g / g solid catalyst. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. After washing twice with hexane, adjusting the total volume to 120, triethyl aluminum 3
After the moles were added, propylene was supplied at a rate of 2130 Nl / hour for 1.5 hours to perform prepolymerization of propylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of propylene was completed, the reactor was closed, polymerization of the remaining propylene was performed for 30 minutes, and the mixture was washed twice with hexane. As a result of the analysis, the amount of prepolymerization by propylene was 2.7 g / g solid catalyst part.

[Polymerization] Propylene was polymerized in the same manner as in Example 1. As a result, the content of poly-3-methyl-1-butene in the produced polypropylene was 220 ppm. A film was prepared in the same manner as in Example 1, and the film was evaluated.

 Table 1 shows the results.

Comparative Examples 1 and 2 Table 1 shows the results of the polymerization in Examples 1 and 2 when propylene prepolymerization was omitted without supplying propylene.

Example 3 A solid titanium catalyst component [A] was prepared in the same manner as in Example 1.

[Preliminary polymerization] Purified hexane 100, triethylaluminum 10 mol, trimethylmethoxysilane 10
Moles of the titanium catalyst component [A] is 1 in terms of titanium atoms.
After addition of 10 kg of mol and 3-methyl-1-butene,
The suspension was maintained at 20 ° C. for 3 hours with stirring,
Preliminary polymerization of methyl-1-butene was performed. As a result of the analysis, the prepolymerized amount of 3-methyl-1-butene was 3.9 g / g solid catalyst. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. After washing twice with hexane, adjusting the total volume to 120, triethyl aluminum 3
After the moles were added, ethylene was supplied at a rate of 3150 Nl / hour for 2 hours to perform prepolymerization of ethylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of ethylene was completed, the reactor was closed, polymerization of residual ethylene was carried out for 30 minutes, and the resultant was washed twice with hexane. As a result of the analysis, the amount of prepolymerization with ethylene was 2.8 g / g solid catalyst part.

[Polymerization] Propylene was polymerized in the same manner as in Example 1. As a result, the content of poly-3-methyl-1-butene in the produced polypropylene was 260 ppm. A film was prepared in the same manner as in Example 1, and the film was evaluated.

 Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing an olefin polymerization catalyst according to the present invention.

Continuation of front page (72) Inventor Akinori Toyoda 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A 1-217014 (JP, A) JP Hei 1-311106 (JP, A) JP-A-2-265905 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] [A] A magnesium, a titanium, a halogen and an electron donor obtained by reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor are essential. Using a solid titanium catalyst component [B] an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst component [X] formed from an electron donor, 0 per gram of solid portion inside.
1 to 300 g of a linear α-olefin having 2 to 5 carbon atoms is prepolymerized, and then 0.1 g / g of the solid portion in the catalyst component.
A method for producing a prepolymerized olefin polymerization catalyst component [Y], which comprises prepolymerizing 1 to 100 g of 3-methyl-1-butene. 2. [A] Magnesium, titanium, a halogen and an electron donor obtained by reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor are essential. A solid titanium catalyst component [B], an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst component [X] formed from an electron donor. 0.1 g per solid portion of
~ 100 g of 3-methyl-1-butene is prepolymerized, and 0.1 to 300 g of carbon atoms of 2 to 0.1 g per 1 g of the solid portion in the catalyst component.
5. A method for producing a prepolymerized olefin polymerization catalyst component [Y], which comprises preliminarily polymerizing the linear α-olefin of No. 5.