JPH08259619A - Production of polyolefin and catalyst - Google Patents

Abstract

PURPOSE: To obtain a polyolefin by polymerizing an α-olefin in the presence of a prescribed solid catalytic component, a titanium compound, etc., having excellent high transparency and image clarity, useful as a molding, etc. CONSTITUTION: A cycloolefin is polymerized in the presence of a solid component obtained by supporting a metallocene compound of the formula [Me is Ti, Zr or Hf; A is a cycloalkanedienyl skeleton-containing mononucleus or polynucleus hydrocarbon; R1 is a 1-4C alkylene, a di-(1-6C alkyl or aryl)silylene, etc.; R2 and R3 are each a halogen, a 1-6C alkyl or an aryl] on a carrier containing Mg and a halogen atom to form a solid catalytic component containing a highly crystalline cycloolefin polymer. An α-olefin is polymerized in the presence of the solid catalytic component, a titanium compound such as titanium tetrachloride and an organoaluminum compound such as triethylaluminum to give the objective polyolefin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a highly transparent polyolefin and a catalyst. More specifically, it relates to a method for producing a crystalline polyolefin containing a small amount of a crystalline cycloolefin polymer and having remarkably improved transparency and image clarity, and a catalyst.

[0002]

2. Description of the Related Art Polypropylene is a resin sheet having excellent mechanical properties, transparency, moldability and chemical stability.
It is widely used as a material for extrusion molded products such as films and blows, and injection molded products. However, transparency,
Because of the high crystallinity of polypropylene, the image clarity is generally inferior to other highly transparent thermoplastic resins such as polystyrene and polyvinyl chloride.

Several proposals have been made so far in an attempt to improve the transparency and image clarity of a polypropylene stretched film or polypropylene sheet. For example, by adding an organic or inorganic nucleating agent such as sorbitol derivative, an alkali metal salt or an aluminum salt of aromatic carboxylic acid, or talc to polypropylene, extrusion of a raw sheet during film formation During the cooling and solidification process of the molten sheet during molding, the spherulites inside the solidified raw sheet become smaller and uniform, the transparency of the sheet itself, the image clarity is improved, and the transparency of the stretched film, It is known that the image clarity is improved.
However, these organic nucleating agents have a problem that they are bleeding from polypropylene during extrusion and cause roll fouling, and odor is generated during processing. Further, there is a problem that bleeding occurs when a sheet, a film or the like is stored for a long period of time. Furthermore, the aromatic carboxylic acid salt itself or its hydrolyzate reacts with other additives, thereby deteriorating the original performance of the additive and coloring polypropylene.

Further, talc, which is well known as an inorganic nucleating agent, causes poor dispersion at the time of compounding, resulting in variations in optical properties such as transparency and image clarity of polypropylene sheets and polypropylene films, and talc formation. There is a problem in that the aggregates cause spots and fish eyes.

On the other hand, attempts have been made to improve transparency by using a copolymer of propylene and α-olefin (see Japanese Patent Publication No. 32430/45). However, it cannot be said that the image clarity is sufficient.

As described above, conventionally, attempts have been made to improve the transparency and image clarity of polypropylene moldings by the above methods, but they are still unsatisfactory. That is, an object of the present invention is to provide a polypropylene resin having excellent transparency and image clarity without the above-mentioned drawbacks.

[0007]

The inventors of the present invention polymerized α-olefins in the presence of a solid catalyst component containing a crystalline cycloolefin polymer obtained by polymerization with a specific catalyst system, a titanium compound and an organoaluminum compound. The inventors have found that the problems of the present invention can be solved by doing so and have proposed the present invention. That is, the present invention provides the following formula (1)

[0008]

Embedded image

(Wherein Me is Ti, Zr or Hf, A is a mononuclear or polynuclear hydrocarbon group having a cycloalkadienyl skeleton, R ₁ is an alkylene group having 1 to 4 carbon atoms, and di). A (C1-6 alkyl or aryl) silylene group or a (C1-6 alkyl) (aryl) silylene group, and R ₂ and R ₃ are the same or different and each is a halogen atom, a C 1 A metallocene compound represented by the formula (6), which is an alkyl group or an aryl group of 6), is supported on a carrier containing magnesium and a halogen atom, and a cycloolefin is polymerized in the presence of a trialkylaluminum to give a high concentration. A solid catalyst component containing a crystalline cycloolefin polymer is formed, and then the above solid catalyst component, titanium compound and organoaluminum are formed. By polymerizing the α-olefin in the presence of a Um compound allowed to generate high through property polyolefins, characterized in that.

The metallocene compound used in the present invention is a compound represented by the above general formula (1). Here, Me is Ti, Zr or Hf, preferably Z
r. A is a mononuclear or polynuclear hydrocarbon group having a cycloalkadienyl skeleton, and R ₁ has 1 to 4 carbon atoms.
Alkylene group, di (C1-6 alkyl) silylene group, or (C1-6 alkyl) (aryl)
It is a silylene group and R ₂ and R ₃ are the same or different and each is a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group.

Specific examples of A include methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, i-propylcyclo group. Examples thereof include a pentadienyl group, a t-butylcyclopentadienyl group, an indenyl group, a methylindenyl group, a dimethylindenyl group, an i-propylindenyl group, a t-butylindenyl group and a fluorenyl group. Specific examples of R ₁ include methylene group, ethylene group, propylene group, butylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, phenylmethylsilylene group and the like. As the halogen atom of R ₂ and R ₃ ,
Chlorine, bromine, iodine and the like, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and the like. Examples of the aryl group include phenyl group and toluyl.

The metallocene compounds that can be preferably used in the present invention include the following. Dimethylmethylenebis (indenyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl)
Zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl) zirconium dichloride.

In the present invention, a carrier carrying the above metallocene compound is essential. When no carrier is used, almost no cycloolefin polymer is produced. As the carrier, one containing magnesium and a halogen atom is used. As the carrier, MgCl ₂ , MgB
r ₂ , MgI ₂ , MgCl (OH), MgBr (OH),
Examples include MgI (OH). Further, the above-mentioned carrier generally has an average particle size of 10 to 300 μm, further 20 to 200 μm, though it varies depending on the type of carrier and the production method.
Specific surface area of 100-1000 m ² / g, further 100-
It is preferably 600 m ² / g.

The method of loading the metallocene compound on the carrier is not particularly limited, but it is preferable to co-grind the metallocene compound and the carrier or to directly contact the carrier and the metallocene compound in a hydrocarbon solvent capable of dissolving the metallocene compound. A ball mill method and a vibration mill method are preferably used as the co-pulverization method. As the hydrocarbon solvent, hexane, heptane, saturated aliphatic hydrocarbons such as octane, cyclopentane, saturated alicyclic hydrocarbons such as cyclohexane,
Aromatic hydrocarbons such as benzene, toluene and xylene can be used. The conditions for loading the metallocene compound on the carrier are not particularly limited, but are usually -20 to 200.
It is carried out by co-milling or contacting at 0.1 ° C. for 0.1 to 100 hours. Preferably 0 to 150 ° C, 0.5 to 5
0 hours. The ratio of the metallocene compound to the carrier is preferably 0.001 to 50 mmol, more preferably 0.01 to 10 mmol, based on 1 gram of the carrier. The components thus obtained can be washed with the above-mentioned hydrocarbon solvent, if necessary.

Next, in the present invention, a trialkylaluminum is used. Compounds other than trialkylaluminum, for example, organoaluminum compounds such as dialkylaluminum monochloride, monoalkyldichloride, trialkoxyaluminum, dialkoxyaluminum monochloride, etc. cannot sufficiently achieve the object of the present invention.

Examples of trialkylaluminum preferably used in the present invention include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-i-propylaluminum, tri-i-butylaluminum, trioctylaluminum and the like.
The amount of trialkylaluminum used is the above solid component 1
The amount is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, per g.

The cycloolefin is polymerized in the presence of the above-mentioned components. Examples of the cycloolefin include cyclobutene, 3,3,4,4-tetramethylcyclobutene, cyclopentene, cyclopentadiene, 4-methylcyclopentene, 4,4-dimethylcyclopentene,
3,3,5,5-tetramethylcyclopentene, cyclohexene, 4-methylcyclohexene, 1,3-dimethylcyclohexene, 1,3-dimethylcyclohexene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, cycloheptene, 1,3-cycloheptadiene,
1,3,5-cycloheptatriene, cyclooctene,
1,5-Cyclooctadiene, cyclododecene and the like are preferably used.

The cycloolefin is polymerized in the above-mentioned hydrocarbon solvent usually at -20 to 100 ° C. for 0.1 to 100 hours.
Preferably, it is performed at 0 to 70 ° C. for 0.5 to 50 hours.
The amount of cycloolefin polymer in the solid catalyst component containing cycloolefin polymer obtained after the polymerization is 1
It is preferable to polymerize the cycloolefin so as to be ˜90 wt%, preferably 5 to 50 wt%. The amount of cycloolefin used is 0.0 per 1 g of the solid catalyst component.
1 to 100 g is preferable, and 0.05 to 10 g is more preferable. The solid catalyst component after the cycloolefin polymerization can be cleaned with the above hydrocarbon solvent, if necessary.

Next, in the present invention, the α-olefin is polymerized in the presence of a solid catalyst component containing a highly crystalline cycloolefin polymer, a titanium compound and an organoaluminum compound. At this time, it is preferable that the solid catalyst component containing the highly crystalline cycloolefin polymer and the titanium compound are brought into contact with each other prior to the polymerization of the α-olefin in order to achieve high activation and high particle property.

The titanium compound to be brought into contact is a trivalent or tetravalent titanium compound, and TiCl is exemplified.
₄ , TiBr ₄ , TiI ₄ , TiCl ₃ , TiBr ₃ , Ti
I ₃ , 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 (Oi-C 4 H 9} ) Br 3, Ti (OCH 3) 2 Cl 2,
_{Ti (OC 2 H 5) 2} Cl 2, Ti (On-C 4 H 9) 2 C
l ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ C
1, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (C ₂ H ₅ ) ₃ Br, T
_{i (OCH 3) 4, Ti} (OC 2 H 5) 4, Ti (On-C 4
H ₉ ) _{4 and the} like, preferably TiCl ₄ and TiCl ₃ .

When the titanium compound is brought into contact, various organic acid esters, organic acid anhydrides, ethers, ketones,
It is also possible to coexist with an electron-donating compound such as a tertiary amine, phosphorous acid ester, phosphoric acid ester, phosphoric acid amide, carboxylic acid amide, or nitrile.

The method of contact is not particularly limited,
For example, a co-milling method and a method of contacting in a hydrocarbon solvent are preferably used. Examples of the co-milling method include a ball mill method and a vibration mill method. As the hydrocarbon solvent, hexane, heptane, saturated aliphatic hydrocarbons such as octane, cyclopentane, saturated alicyclic hydrocarbons such as cyclohexane,
Aromatic hydrocarbons such as benzene, toluene and xylene can be used. The contact condition of each component is −20 to 200 ° C.,
0.1 to 100 hours, preferably 0 to 150 ° C, 0.5 to
It is preferable to adopt it for 50 hours. The proportion of the solid catalyst component and the titanium compound, and the electron donor that can coexist as necessary, is 0.1 to 10000 mmol, preferably 1 to 1000 mmol, of the titanium compound per 1 gram of the solid catalyst component. 0.01 ~
It is 10 mmol, preferably 0.1 to 5 mmol.
The solid catalyst component after contact with the titanium compound can be washed with the above-mentioned hydrocarbon solvent, if necessary. It is also possible to dry after washing.

The solid catalyst component obtained by the above method contains 1 to 90% by weight of a cycloolefin polymer as an essential component and 0.05 to 5% by weight of a titanium compound as a titanium atom, and an electronic component as an optional component. Donating compound 0.1
It is preferable to contain 10 to 10% by weight.

Organoaluminum compounds used in the polymerization of α-olefins include, for example, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-nhexylaluminum, tri-noctylaluminum,
Examples thereof include trialkylaluminums such as tri-decylaluminum; dialkylaluminum monohalides such as diethylaluminum monohalide; and alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride and ethylaluminum dichloride. Other alkoxyaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used. Of these, trialkylaluminums such as trimethylaluminum and triethylaluminum are preferable.

As the α-olefin which can be used in the main polymerization, ethylene and α-olefin having 3 to 20 carbon atoms,
For example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

If desired, the above-mentioned electron donor or organosilicon compound may be allowed to coexist during the α-olefin polymerization. Specific examples of the organic silicon compound include dimethyldimethoxysilane, diethyldimethoxysilane,
Dipropyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, isopropyltriethoxy Examples thereof include silane, hexyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane and allyltriethoxysilane.

In the present invention, as the polymerization method and the polymerization conditions of the α-olefin, known polymerization methods such as slurry polymerization, gas phase polymerization and solution polymerization are adopted without any limitation. Further, either continuous or discontinuous polymerization may be used. In the case of propylene, the olefin pressure of the reaction system is normal pressure to 50 kg / cm ² G
And the reaction temperature is 0 to 100 ° C., preferably 10 to
It is in the range of 80 ° C. Although the reaction time can be appropriately determined, it is usually adopted in the range of 1 to 24 hours.

The proportion of the solid catalyst component, the organoaluminum compound and the electron donor or the organosilicon compound used in the α-olefin polymerization is 1 to 100 per 100 g of titanium atom in the solid catalyst of the organoaluminum compound.
0 mol, preferably 10 to 500 mol, 0.01 to 10 mol, preferably 0.05 to 1 mol of electron donor or organosilicon compound per mol of organoaluminum.
Is.

[0029]

INDUSTRIAL APPLICABILITY According to the present invention, a crystalline catalyst is prepared by polymerizing a cycloolefin in the presence of a trialkylaluminum, a solid catalyst component obtained by supporting a specific metallocene compound on a carrier containing magnesium and a halogen atom. Forming a solid catalyst containing an olefin polymer,
Then, a highly transparent polyolefin can be produced by polymerizing the olefin in the presence of the solid catalyst component, the titanium compound and the organoaluminum compound.

[0030]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The resins obtained in the following Examples and Comparative Examples were evaluated by the following methods. (1) Haze It was measured according to JIS K 6714. (2) Image value An optical comb of 0.1 is used with an image measuring device manufactured by Suga Test Instruments Co., Ltd.
25 mm was used, and the comb value was measured by the transverse stretching method in the case of a biaxially stretched film, and in the case of a sheet in parallel with the extrusion direction, and the image value was measured.

Example 1 [Preparation of solid catalyst component] Under a nitrogen stream, 15 g of anhydrous magnesium chloride and 630 mg of ethylenebis (indenyl) zirconium dichloride were pulverized with a vibration mill for 48 hours. The obtained solid component was washed 3 times with 100 ml of toluene to obtain a solid component carrying the metallocene compound. Zirconium contained in this solid component is 0.08 mmol /
g. Then add toluene 5 to a 100 ml flask.
0 ml, cyclopentene 30 ml, toluene solution of triisobutylaluminum (1 mmol / ml) 10 ml
Then, 10 g of the solid component synthesized above was introduced and polymerization was carried out at 50 ° C. for 8 hours. After completion of the polymerization, the supernatant was removed and the residue was washed 3 times with 100 ml of toluene to obtain a solid catalyst component containing polycyclopentene.

[Contact with Titanium Compound] The solid catalyst component obtained above was added with 2 ml of diisobutyl phthalate and 2 ml of titanium tetrachloride and pulverized with a vibration mill for 48 hours. After the pulverization was completed, the co-pulverized product was transferred to a 200 ml flask, 100 ml of toluene was added, the temperature was raised to 100 ° C., the mixture was stirred for 30 minutes, and then the supernatant was removed. Then n-hexane 100
It was washed 5 times with ml to obtain a solid catalyst component containing a titanium component. The obtained solid catalyst component is polycyclopentene 2
It contained 8.5 wt% and 1.43 wt% titanium.

[Polymerization of propylene] 450 g of propylene and triethylaluminum (1 mmol / ml hexane solution) were placed in a stainless steel autoclave with an internal volume of 2 liters.
1 ml, cyclohexylmethyldimethoxysilane (0.
1 mmol / ml) 1 ml was added and the internal temperature was raised to 70 ° C. After the temperature was raised, 15 mg of a solid catalyst component containing polycyclopentene and a titanium component was pressed into the system to start polymerization, and polymerization was carried out at 70 ° C. for 1 hour. Polymerization was stopped by purging propylene in the system, and the obtained polymer was dried at 70 ° C. for 4 hours. The amount of polymer produced was 150 g. Calculated from the content of polycyclopentene contained in the solid catalyst component, this polypropylene had 28.5 p
pm polycyclopentene was included.

Example 2 Polycyclopentene was prepared in the same manner as in Example 1 except that methylenebis (indenyl) zirconium dichloride was used in place of ethylenebis (indenyl) zirconium dichloride in the preparation of the solid catalyst component of Example 1.
A solid catalyst component containing a titanium component was obtained. The obtained solid catalyst component was polycyclopentene 19.3 wt% and titanium 1.
It contained 69 wt%. The propylene obtained by polymerizing propylene by the same operation as in Example 1 using this solid catalyst component was 183 g, which was calculated from the polycyclopentene content in the solid catalyst component to be 15. It contained 8 ppm of polycyclopentene.

Example 3 Polycyclopentene was prepared in the same manner as in Example 1 except that dimethylsilylenebis (indenyl) zirconium dichloride was used in place of ethylenebis (indenyl) zirconium dichloride in the preparation of the solid catalyst component of Example 1. A solid catalyst component containing a titanium component was obtained. The obtained solid catalyst component was polycyclopentene 20.6 wt.
%, Titanium 1.74 wt%. Further, propylene was polymerized by the same operation as in Example 1 using this solid catalyst component to obtain 169 g of polypropylene, and 18.18 in this polypropylene was calculated from the content of polycyclopentene contained in the solid catalyst component. 2 ppm
Contained polycyclopentene.

Example 4 Polycyclopentene was prepared in the same manner as in Example 1 except that triethylaluminum was used in place of triisobutylaluminum in the preparation of the solid catalyst component of Example 1.
A solid catalyst component containing a titanium component was obtained. The obtained solid catalyst component contained 18.6 wt% of polycyclopentene and 1.6 wt% of titanium. Further, propylene was polymerized by the same operation as in Example 1 using this solid catalyst component to obtain 172 g of polypropylene, and the polypropylene was 16. It contained 2 ppm of polycyclopentene.

Example 5 A solid catalyst component containing polycyclopentene and a titanium component was prepared in the same manner as in Example 1 except that Mg (OH) Cl was used in place of magnesium chloride in the preparation of the solid catalyst component of Example 1. Got The obtained solid catalyst component contained 15.6 wt% of polycyclopentene and 1.8 wt% of titanium. The polypropylene obtained by polymerizing propylene using this solid catalyst component in the same manner as in Example 1 weighed 152 g, and was calculated from the content of polycyclopentene contained in the solid catalyst component to be 15. It contained 3 ppm of polycyclopentene.

Comparative Example 1 Cyclopentene was polymerized by the same procedure as in Example 1 except that diisobutylaluminum chloride was used in place of triisobutylaluminum in the preparation of the solid catalyst component of Example 1, but no polymer was obtained. There wasn't.

Comparative Example 2 Cyclopentene was polymerized in the same manner as in Example 1 except that cyclopentadienyl zirconium dichloride was used in place of ethylenebis (indenyl) zirconium dichloride in the preparation of the solid catalyst component of Example 1. However, only a trace amount of the polymer was obtained.

Comparative Example 3 Cyclopentene was polymerized in the same manner as in Example 1 except that magnesium chloride was not used in the preparation of the solid catalyst component of Example 1, but no polymer was obtained.

Comparative Example 4 A solid catalyst component was obtained by the same procedure as in Example 1, except that the cyclopentene polymerization operation was not carried out. The titanium content in the obtained solid catalyst component was 2.0 wt%. Further, polypropylene was obtained by polymerizing propylene using the solid catalyst component in the same manner as in Example 1 to obtain 230 g of polypropylene.

Example 6 A solid catalyst component containing polycyclobutene and a titanium component was obtained by the same operation except that cyclobutene was used instead of cyclopentene in the preparation of the solid catalyst component of Example 1.
The obtained solid catalyst component was polycyclobutene 15.3 wt.
%, And 1.50 wt% titanium. Further, propylene was polymerized by the same operation as in Example 1 using this solid catalyst component to obtain 182 g of polypropylene, and it was calculated from the content of polycyclobutene contained in the solid catalyst component to obtain 23 It contained 0.0 ppm of polycyclobutene.

Example 7 A solid catalyst component containing polycyclopentene and a titanium component was obtained in the same manner as in Example 1 except that titanium trichloride was used instead of titanium tetrachloride in the contact with the titanium compound of Example 1. It was The obtained solid catalyst component contained 9.8 wt% of polycyclopentene and 1.50 wt% of titanium. The polypropylene obtained by polymerizing propylene using this solid component in the same manner as in Example 1 was 152 g, and 9.6 ppm in this polypropylene was calculated from the content of polycyclopentene contained in the solid catalyst component.
Contained polycyclopentene.

Example 8 A solid catalyst component containing polycyclobutene and a titanium component was obtained by the same operation except that cyclobutene was used in place of cyclopentene in Example 7. The obtained solid catalyst component contained 8.3 wt% of polycyclobutene and 1.68 wt% of titanium. The polypropylene obtained by polymerizing propylene using this solid catalyst component in the same manner as in Example 1 was 193 g, and it was calculated from the content of polycyclobutene contained in the solid catalyst component. It contained 0.4 ppm of polycyclobutene.

Example 9 Propylene-ethylene random copolymerization was carried out in place of propylene homopolymerization in Example 1, and ethylene was reduced to 0.
175 g of a copolymer containing 5 mol% was obtained. The copolymer contained 24.4 ppm of polycyclopentene calculated from the content of polycyclopentene contained in the solid catalyst component.

Example 10 Propylene-ethylene random copolymerization was carried out in place of propylene homopolymerization in Example 7, and ethylene was reduced to 0.
162 g of a copolymer containing 5 mol% was obtained. The copolymer contained 9.0 ppm of polycyclopentene calculated from the content of polycyclopentene contained in the solid catalyst component.

Example 11 Propylene-butene-1 random copolymerization was carried out in place of propylene homopolymerization in Example 1 to obtain 177 g of a copolymer containing butene-1 at 0.8 mol%. The copolymer contained 24.1 ppm of polycyclopentene calculated from the content of polycyclopentene contained in the solid catalyst component.

Example 12 Propylene-butene-1 random copolymerization was carried out in place of propylene homopolymerization in Example 7 to obtain 157 g of a copolymer containing butene-1 in an amount of 0.8 mol%. This copolymer contained 9.3 ppm of polycyclopentene calculated from the content of polycyclopentene contained in the solid catalyst component.

Comparative Example 5 Propylene-ethylene random copolymerization was carried out instead of propylene homopolymerization in Comparative Example 4 to obtain 265 g of a copolymer containing 0.5 mol% of ethylene.

Comparative Example 6 In Comparative Example 4, propylene-butene-1 random copolymerization was carried out instead of propylene homopolymerization to give butene-1.
235 g of a copolymer containing 0.8 mol% of was obtained.

Example 13 [Evaluation of Resin] (Granulation) 100 parts by weight of polypropylene produced in Examples 1 to 12 and Comparative Examples 4 to 6 were mixed with 2,6-as an antioxidant.
After adding 0.1 part by weight of di-t-butylhydroxytoluene and 0.1 part by weight of calcium stearate as a chlorine scavenger and mixing with a Henschel mixer for 5 minutes, 230 g of a screw diameter 65 mmφ extruder was used. The mixture was extruded at 0 ° C. and the pellets were granulated to obtain raw material pellets.

(Formation of Biaxially Stretched Film) Using the obtained polypropylene resin composition pellets, a film formation experiment of a biaxially stretched film was carried out by the following method. The polypropylene resin composition pellets were extruded at 280 ° C. using a T-die sheet extruder having a screw diameter of 90 mmφ, and a sheet having a thickness of 2 mm was formed with a cooling roll at 30 ° C. Then
This sheet was longitudinally stretched at 150 ° C. by 4.6 times in a longitudinal direction using a tenter type sequential biaxial stretching device, and subsequently transversely stretched at a mechanical ratio of 10 times in a tenter at 165 ° C. Heat treated with 8% relaxation, thickness 50μ
m biaxially oriented polypropylene film was molded at a speed of 16 m / min. The obtained film was measured for haze and image value 48 hours after molding. The results are shown in Table 1.

[0053]

[Table 1]

(Preparation of Unstretched Sheet) A sheet extrusion molding experiment was conducted by the following method using the pelletized polypropylene resin composition pellets. The raw material pellets are extruded at a resin temperature of 230 ° C. after the die discharge using a T-die extruder having a screw diameter of 40 mmφ, a cooling roll having an outer diameter of 150 mmφ is used, a cooling roll temperature of 20 ° C., a take-up speed of 5 m / min, and a thickness of 1.0 mm. Sheet was molded. The resulting sheet was measured for haze and image value 48 hours after molding. The results are shown in Table 2.

[0055]

[Table 2]

[Brief description of drawings]

FIG. 1 is a flow chart showing a typical procedure of a method for producing a polyolefin of the present invention.

Claims (2)

[Claims] 1. The following formula (1): (Here, Me is Ti, Zr or Hf, A is a mononuclear or polynuclear hydrocarbon group having a cycloalkadienyl skeleton, R ₁ is an alkylene group having 1 to 4 carbon atoms,
A di (C1-C6 alkyl or aryl) silylene group or a (C1-C6 alkyl) (aryl) silylene group, and R ₂ and R ₃ are the same or different and each is a halogen atom, a C 1 ~ 6 alkyl groups or aryl groups. The metallocene compound represented by) is supported on a carrier containing magnesium and a halogen atom, and a cycloolefin is polymerized in the presence of a trialkylaluminum and a solid component containing a highly crystalline cycloolefin polymer. A method for producing a polyolefin, which comprises forming a catalyst component, and then polymerizing the α-olefin in the presence of the solid catalyst component and a titanium compound and an organoaluminum compound to produce a highly transparent polyolefin. 2. The following formula (1): (Here, Me is Ti, Zr or Hf, A is a mononuclear or polynuclear hydrocarbon group having a cycloalkadienyl skeleton, R ₁ is an alkylene group having 1 to 4 carbon atoms,
A di (C1-C6 alkyl or aryl) silylene group or a (C1-C6 alkyl) (aryl) silylene group, and R ₂ and R ₃ are the same or different and each is a halogen atom or a C 1 ~ 6 alkyl or aryl. ) Containing a highly crystalline cycloolefin polymer obtained by polymerizing a cycloolefin in the presence of a solid component having a metallocene compound represented by the formula (3) supported on a carrier and a trialkylaluminum,
Highly transparent polyolefin production catalyst.