JPH1087718A - Catalyst for polymerizing olefin and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst, having high catalytic activities and capable of providing a polymer, hardly containing fine particles and excellent in powder properties by using specific hollow particles as a principal component. SOLUTION: This catalyst consists essentially of (A) hollow particles, preferably hollow spherical particles having <=1,000μm particle diameter, (B) a group IVB transition metallic compound and (C) an organoaluminumoxy compound. Furthermore, the component A is preferably hollow spherical particles formed of primary particles having <=100μm particle diameter and secondary particles, capable of bonding to the primary particles and having <=50μm particle diameter. For example, dimethylsilylbis(2,3,5-trimethylcyclopentadienyl)hafnium dichloride is preferably used as the component B and, e.g. a modified methylaluminoxane is preferably used as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, a novel olefin polymerization catalyst using hollow particles as a carrier, and a method for producing an olefin polymer using the olefin polymerization catalyst, particularly in the present production method, the obtained polymer is a polymer The present invention relates to a method for producing an olefin polymer having almost no fine particles and excellent in powder properties.

[0002]

2. Description of the Related Art As a catalyst for olefin polymerization, a so-called Kaminski catalyst is well known. For example, JP-A-58-19309 discloses that when polymerization of ethylene or copolymerization of ethylene and an α-olefin is carried out using a catalyst comprising a metallocene compound and an organic aluminum oxy compound, an olefin polymer is obtained with high activity. It is disclosed. In this method, the activity per transition metal is high, but the activity per aluminum is low because a large amount of aluminoxane is used. as a result,
There are process problems such as the necessity of removing aluminum in the subsequent process, and economic problems such as an increase in production cost due to the high cost of the aluminoxane used.

[0003] Further, when the olefin higher than propylene is polymerized by using the catalyst system of the present invention, the resulting polymer becomes atactic without stereoregularity, so that the range of application of the catalyst is limited. There is.

The following inventions have been proposed as methods for improving the polymerization activity per aluminum. That is, in the example of JP-A-60-130604, the amount of aluminoxane added was determined by adding triethylaluminum as an organic aluminum to a catalyst system comprising bis (cyclopentadienyl) titanium dichloride and chloroaluminoxane as a transition metal compound. It is described that even when the amount is reduced, the same high activity as before the reduction is exhibited. However, not only industrially satisfactory activity is still not obtained, but also the polypropylene obtained in this system is atactic and does not show any stereoregularity at all.

A method for obtaining a stereoregular polymer has been realized by changing the structure of a ligand (Japanese Patent Laid-Open No. 61-13 / 1986).
0314, JP-A-63-295607, JP-A-1-30
1704, JP-A-2-41303). However, in these techniques, since both the metallocene compound and the organic aluminum oxy compound, which are the catalyst components, are soluble in the reaction system, only a polymer having a very fine particle diameter can be obtained, and the polymer cannot be produced industrially efficiently. Things. In addition, the resulting polymer having a small particle size accumulates on the walls of the reactor and on the stirrer during the polymerization, which makes it difficult to control the polymerization temperature and causes a problem in the operation of the reactor.

In order to solve these problems, there has been proposed a technique for performing olefin polymerization using a catalyst in which one or both of a transition metal compound and an organic aluminum oxy compound are supported on a particulate carrier. ing.
For example, as a method for supporting a catalyst on an inorganic oxide carrier such as silica, silica-alumina, and alumina, JP-A-61-108610, JP-A-61-276805, and JP-A-61-276805.
296008, 63-22804, 63-2807
03, 63-51407, 63-54403, 6
3-81010, 63-66206, 63-895
05, 63-152608, 63-213504,
63-248803 discloses various inventions.
However, the activity of these catalysts is low, and furthermore, inorganic oxides remain in the polymer, which causes deterioration of polymer quality, for example, deterioration of moldability and fish eyes.

On the other hand, as a method using an organic polymer as a carrier, JP-A-63-92621 and JP-A-63-260903 disclose methods.
Inventions and the like have been proposed. When these organic polymers are used as a carrier, the quality of a product polymer can be prevented from lowering as compared with the case where an inorganic oxide is used as a carrier. However, the organic polymer carrier is less likely to carry the catalyst component than the inorganic carrier, so that the activity of the obtained catalyst is low, and the desorption of the catalyst component from the carrier occurs. And it becomes difficult to obtain a polymer having excellent powder properties.

[0008] Various improvements have been made to suppress the production of fine particles of the polymer product. For example, Japanese Unexamined Patent Publication
In 145238, only the co-catalyst methylaminoxan (MAO) is supported on an inorganic oxide containing adsorbed water,
It is disclosed that by combining with a catalyst component comprising a transition metal compound and an organoaluminum compound, a highly active catalyst can be obtained and a polymer having a small number of fine particle components can be obtained. However, the results are not always satisfactory, and it is expected that the properties of the product polymer will change significantly depending on the polymerization conditions.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above.
An object of the present invention is to provide an olefin polymerization catalyst having high catalytic activity, and to obtain an olefin polymerization catalyst in which the obtained polymer is excellent in powder properties and contains almost no fine particles. An object of the present invention is to provide a method for producing a polymer.

[0010]

In order to achieve the above object, the present invention comprises the following components: (A) hollow particles, (B) IV
The present invention proposes an olefin polymerization catalyst comprising a group B transition metal compound and an organic aluminum oxy compound (C) as main components.
The following hollow spherical particles, the hollow particles having a particle size of 100
μm or less primary particles, and a particle size of 5
This includes hollow spherical particles composed of secondary particles of 0 μm or less, and that the olefin is propylene.

The present invention is also a method for producing an olefin polymer, comprising polymerizing an olefin using the above-mentioned catalyst for olefin polymerization.

The present invention is characterized in that hollow particles are used as components of the catalyst. The reason for the excellent effects specific to the present invention has not been clearly elucidated at present, but is presumed to be as follows.

That is, a catalyst produced using a conventionally used carrier such as silica is composed of a catalyst component (organometallic compound,
And MAO) are physically adsorbed and supported on the carrier surface. When polymerization is carried out using this catalyst in a soluble solvent such as toluene, the catalyst component is peeled off and dissolved from the carrier, so that it is considered that fine polymer powder is generated and adheres to the vessel wall. On the other hand, when hollow particles are used as a carrier as in the present invention, each component of the catalyst is sealed off inside and is less likely to be released from the carrier, thereby reducing the production of polymer fine powder, It seems that the powder morphology can be controlled.

Hereinafter, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The hollow particles of the catalyst component (A) used in the present invention are hollow particles, the outside of which is covered with a shell, and the inside of which is a liquid, solid or gas called a core substance. Occupied. The shell is composed of an inorganic compound or an organic compound described later, and may be composed of an inorganic or organic compound alone or both of an inorganic and an organic compound.

The outer shape of the hollow particles is not particularly limited, but is preferably substantially spherical. The average diameter is 1000 μm or less, and particularly preferably 300 to 800 μm.

The diameter of the hollow portion is 1 to 9 times the diameter of the hollow particles.
It is 9%, particularly preferably 10-90%, most preferably 30-80%.

Preferred inorganic compounds constituting the shell include:
SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , Ti
Single oxides such as O ₂ , ZrO ₂ , and Fe ₂ O ₃ and double oxides thereof, and hydroxide salts such as Ni (OH) ₂ ;
Carbonates such as Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ and MgCO ₃ ; sulfates such as Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ and BaSO ₄ ; KNO ₃ , Mg (NO ₃ ) ₂ ; A nitrate such as Al ₂ (NO ₃ ) ₃ can be exemplified.

As described above, these inorganic compounds may be used alone or as a mixture of two or more. Further, the shell may be formed from two or more types of particles having different particle sizes. Specifically, it may be formed of relatively large particles having a particle size of 100 μm or less and relatively fine particles of 50 μm or less that combine the particles. The large particles and the fine particles may be the same substance or different substances. By varying the ratio between the large particles and the fine particles, the size of the voids between the particles constituting the shell can be arbitrarily adjusted.

As the method for producing the hollow particles comprising the inorganic compound, there are an interfacial reaction method formed on spherical oil droplets (for example, Journal of the Society of Color Materials, 507-11, (1977)) and a method formed on a solid. Powder bed method (for example, industrial materials, 20, 91
-95, (1972)) and the like.

The interfacial reaction method is a chemical technique, which forms a spherical shell by utilizing the property that fine particles adhere to the interface between water and oil, and then extracts and removes the core substance oil with ethanol or the like. This is a method for producing hollow particles. More specifically, a solution in which primary particles are dispersed in water is placed in an organic solvent that does not mix with water, and is stirred at high speed to form spherical oil droplets and adhere the primary particles to the oil droplets. A secondary particle is generated in a void portion of the primary particle by adding a component for generating a secondary particle, and this acts as a binder. Thereafter, the oil phase is extracted using ethanol or the like, and hollowed out.

In the powder bed method, a solid having a low melting point is used as a core substance,
The raw material powder mixed with a suitable binder is coated and granulated on the outside of the core material, and then the core material is thermally decomposed by heating and hollowed to produce hollow particles. Thereafter, generally, a method is adopted in which the spherical shell is strengthened by sintering or melting the spherical shell portion by further heating at a high temperature.

The organic compound constituting the shell is preferably a natural polymer or a synthetic polymer. Preferred natural polymers include gelatin and the like, and gum arabic, sodium alginate, carboxymethyl cellulose, carrageenan and the like may be mixed therewith. Preferred synthetic polymers include polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polystyrene, polyvinyl acetate, polyacrylate, ethyl cellulose, and the like, and these may be used alone or in combination. it can.

Methods for producing hollow particles using an organic compound include a chemical production method, a physical production method, and a mechanical production method.

As the chemical production method, there is an interfacial polymerization method (for example, Journal of the Society of Powder Technology, 24, 474-479 (1987)) utilizing the polymer synthesis reaction at the water-oil interface as it is. Examples of monomers used in the interfacial polymerization method include addition-polymerizable ones such as vinyl chloride, vinylidene chloride, acrylonitrile, styrene, vinyl acetate, acrylates and methacrylates, and polyamines, glycols, polyhydric phenols, and polyhydric phenols. Examples include polycondensable ones such as esters. These may be used alone or as a mixture of two or more. Further, a cross-linking agent may be mixed to cross-link the polymers.

As a physical production method, there is a core solvation method utilizing phase separation (for example, Industrial Materials 17, 13-23 (1969)). The core solvation method comprises mixing, dispersing and emulsifying a shell material and a core material that are not mixed with each other, and then curing the shell material.

The core substance may be any of solid, liquid and gas. However, when an aqueous solution is used as the solvent, the core substance is a hydrophobic substance, and the shell substance is a hydrophilic polymer such as gelatin. preferable. When an organic solvent is used as the solvent, any of a hydrophilic substance and a hydrophobic substance can be used as the core substance, as long as the substance does not dissolve in the solvent. Polymers are available.

Specific examples of the core substance used in the physical production method include hydrocarbon compounds such as hexane, heptane and petroleum benzyl; oils and fats such as olive oil; alcohols such as ethanol and propanol; esters such as ethyl acetate;
Ethers such as diethyl ether and isopropyl ether;

Specific examples of the shell material used in the physical production method include cellulose, ethyl cellulose, benzyl cellulose, acetobutyrate, polyethylene,
Examples include polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, rubber, polyvinyl acetate, and styrene-maleic acid copolymer.

The transition metal compound of component (B) used in the present invention is preferably a transition metal complex of Group IVB of the periodic table represented by the following general formula (1).

[0031]

Embedded image In the general formula (1), M represents a group IVB transition metal made of titanium, zirconium or hafnium. Y represents silicon, germanium, tin or a hydrocarbon group having 1 to 10 carbon atoms, and R ² may be the same or different, and represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.

[0032] R ² ₂ Y are bridging the two cyclopentadienyl rings. Specific examples of the crosslinking portion R ² ₂ Y, a methylene group, an alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, an alkylidene group such as diphenylmethylidene group, dimethylsilylene Group, diethylsilylene group, dipropylsilylene group, diisopropylsilylene group, silicon-containing cross-linking group such as diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, dimethylgermylene group, diethylgermylene group, dipropylgermylene Group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, germanium-containing crosslinking group such as methylphenylgermylene group, dimethylstannylene group, diethylstannylene group, dipropylstannylene group, diisopropyls Ylene group, diphenyl stannyl alkylene group, methylethyl stannyl alkylene group, tin-containing crosslinking group such as methyl phenyl stannyl alkylene group.

(R ¹ _n -C ₅ H _4-n ) and (R ¹ _m -C ₅ H
_4-m ) represents an unsubstituted or substituted cyclopentadienyl group, and n and m are integers of 0 to 4. Each R ¹ may be the same or different, and represents hydrogen, a silyl group or a hydrocarbon group. Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, and octyl. , Nonyl, decyl, phenyl, benzyl, naphthyl, etc.
20 hydrocarbon groups, methoxy, ethoxy, propoxy,
An alkoxy group having 1 to 10 carbon atoms such as butoxy, C such as phenoxy, methylphenoxy, and pentamethylphenoxy
Aryloxy group having ₆ -C _20, trimethylsilyl, a silyl group such as triethylsilyl.

When two R ¹ are bonded to two carbons adjacent to each other on a cyclopentadienyl ring,
The two R ¹ may combine with each other to form a carbocyclic ring of 4 to 6 carbon atoms. Examples of the formation of the carbocycle include an indenyl group, a tetrahydroxyindenyl group, a fluorenyl group, a tetrahydroxyfluorenyl group, and an octahydroxyfluorenyl group. Further, a substituent such as a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms can be introduced on the carbon ring.

X ¹ and X ² may be the same or different,
Shows a hydrogen, halogen or hydrocarbon group. Specific examples of X ¹ and X ² include halogen groups such as fluorine, chlorine, bromine and iodine, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, naphthyl,
And C1-20 hydrocarbon groups; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; and aryloxy groups such as phenoxy, methylphenoxy and pentamethylphenoxy.

The above-mentioned transition metal compounds are exemplified without limitation.

As an example of the compound of the general formula (1), those in which the crosslinked portion is silicon and X ¹ and X ² are halogen are dimethylsilylbis (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene Screw (2, 4-
(Diethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-triethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-di-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene Bis (2,3,5-tri-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-diisopropylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,
5-triisopropylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-din
-Butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-tri-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-diisobutylcyclopentadienyl) zirconium dichloride, dimethyl Silylene bis (2,3,5-triisobutylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,4-ditert-butylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene bis (2,
3,5-tri-tert-butylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene bis (2,
4-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-triphenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2-
Methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-
Methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2-
Ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (t-
(Butylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methylcyclopentadienyl)
(T-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,
7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,4
-Dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-ethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-n-propylindenyl) zirconium dichloride, dimethylsilylenebis (2- Methyl-
4-isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-n-butylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-tert-butylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3- Methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, dimethylsilylene (3-n-
Propylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-n-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, and the like.

Examples of the compound in which the crosslinked portion is silicon and X ¹ and X ² are hydrocarbon groups include dimethylsilylbis (2-methylcyclopentadienyl) zirconium dimethyl and dimethylsilylbis (3-methylcyclopentane Dienyl)
Zirconium dimethyl, dimethylsilylene bis (2, 4
-Dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,4-diethylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis ( 2,3,5-triethylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,4-di-n-propylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,3,5-tri-n-propylcyclo) Pentadienyl) zirconium dimethyl,
Dimethylsilylenebis (2,4-diisopropylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,3,5-triisopropylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (2,4-ditert-butylcyclo) Pentadienyl) zirconium dimethyl, dimethylsilylenebis (2,3,5-tritert-butylcyclopentadienyl) zirconiumdimethyl, dimethylsilylenebis (indenyl) zirconiumdimethyl, dimethylsilylenebis (4,5,6,7- Tetrahydroindenyl) zirconium dimethyl, dimethylsilylenebis (2-methylindenyl) zirconiumdimethyl, dimethylsilylenebis (2,4-dimethylindenyl) zirconiumdimethyl, dimethylsilylene (2-methyl-4-ethylindenyl) zirconium dimethyl, dimethylsilylenebis (2-methyl-4-n-propylindenyl) zirconium dimethyl, dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dimethyl Dimethylsilylenebis (2-methyl-4-n-butylindenyl) zirconium dimethyl, dimethylsilylenebis (2-methyl-4-tert-butylindenyl) zirconium dimethyl, dimethylsilylenebis (2
-Methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconiumdimethyl, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dimethyl, dimethylsilylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylsilylene (3-n-propylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylsilylene (3-isopropylcyclopentadienyl) (Fluorenyl) zirconium dimethyl, dimethylsilylene (3-n-butylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylsilylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dimethyl, and the like.

The crosslinked portion is a germanium compound,
Examples of the compound in which X ¹ and X ² are halogen include dimethylgermylene bis (2-methylcyclopentadienyl)
Zirconium dichloride, dimethylsilylbis (3-
Methylcyclopentadienyl) zirconium dimethyl,
Dimethylgermylene bis (2,4-dimethylcyclopentadienyl) zirconium dimethyl, dimethylgermylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dimethyl, dimethylgermylene bis (2,4-diethylcyclopenta Dienyl) zirconium dimethyl, dimethylgermylene bis (2,3,5-triethylcyclopentadienyl) zirconium dimethyl, dimethylgermylene bis (2,4-di-n-propylcyclopentadienyl) zirconium dimethyl, dimethylgermylene Bis (2,3,5-tri-n-propylcyclopentadienyl) zirconium dimethyl, dimethylgermylene bis (2,4-diisopropylcyclopentadienyl) zirconium dimethyl, dimethylgermylene bis (2,3,5-trii Propyl cyclopentadienyl) zirconium dimethyl, dimethyl gel Mi Len bis (2,4-di-tert- butyl-cyclopentadienyl)
Zirconium dimethyl, dimethylgermylene bis (2,
3,5-tri-tert-butylcyclopentadienyl)
Zirconium dimethyl, dimethylgermylene bis (indenyl) zirconium dimethyl, dimethylgermylene bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylgermylenebis (2-methylindenyl) zirconium dimethyl, dimethylgermylene Bis (2,4-dimethylindenyl) zirconium dimethyl, dimethylgermylene bis (2-methyl-4-ethylindenyl) zirconium dimethyl, dimethylgermylene bis (2-methyl-4-n-propylindenyl) zirconium dimethyl Dimethylgermylene bis (2-methyl-4-isopropylindenyl) zirconium dimethyl, dimethylgermylene bis (2-methyl-
4-n-butylindenyl) zirconium dimethyl, dimethylgermylene bis (2-methyl-4-tert-butylindenyl) zirconium dimethyl, dimethylgermylene bis (2-methyl-4-phenylindenyl) zirconium dimethyl, dimethyl Germylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylgermylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylgermylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dimethyl, Dimethylgermylene (3-n-propylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylgermylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dimethyl Chill, dimethylgermylene (3
-N-butylcyclopentadienyl) (fluorenyl)
Zirconium dimethyl, dimethylgermylene (3-te
rt-butylcyclopentadienyl) (fluorenyl)
Zirconium dimethyl and the like.

Examples of compounds in which the crosslinked portion is a tin compound and X ¹ and X ² are halogen include dimethylstannylenebis (2-methylcyclopentadienyl) zirconium dichloride and dimethylsilylbis (3-methylcyclohexane). Pentadienyl) zirconium dimethyl, dimethylstannylenebis (2,4-dimethylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,3,
5-trimethylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,4-diethylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,3,5-triethylcyclopentadienyl) zirconium dimethyl, dimethyl Stannylene bis (2,4-di-n-propylcyclopentadienyl)
Zirconium dimethyl, dimethylstannylene bis (2,
3,5-tri-n-propylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,4-
Diisopropylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,3,5-triisopropylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (2,4-ditert-butylcyclopentadienyl) zirconium dimethyl Dimethylstannylenebis (2,3,5-tritert-butylcyclopentadienyl) zirconium dimethyl, dimethylstannylenebis (indenyl) zirconium dimethyl, dimethylstannylenebis (4,5,6,7-tetrahydroindenyl) ) Zirconium dimethyl, dimethylstannylenebis (2-methylindenyl) zirconium dimethyl, dimethylstannylenebis (2,4-dimethylindenyl) zirconium dimethyl, dimethylstannylenebis (2-methyl Ethyl-indenyl) zirconium dimethyl, dimethyl stannyl Len bis (2-methyl -
4-n-propylindenyl) zirconium dimethyl,
Dimethylstannylenebis (2-methyl-4-isopropylindenyl) zirconium dimethyl, dimethylstannylenebis (2-methyl-4-n-butylindenyl) zirconium dimethyl, dimethylstannylenebis (2-methyl-4-tert) -Butylindenyl) zirconium dimethyl, dimethylstannylenebis (2-methyl-4-
Phenylindenyl) zirconium dimethyl, dimethylstannylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylstannylene (2-
Methylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylstannylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylstannylene (3-n-propylcyclopentadienyl) (fluorenyl) zirconium dimethyl, Dimethylstannylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dimethyl,
Dimethylstannylene (3-n-butylcyclopentadienyl) (fluorenyl) zirconium dimethyl, dimethylstannylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dimethyl and the like can be mentioned.

Examples of compounds in which the cross-linking portion is a hydrocarbon group and X ¹ and X ² are halogen include methylene bis (2-
Methylcyclopentadienyl) zirconium dichloride, methylenebis (3-methylcyclopentadienyl)
Zirconium dichloride, methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride,
Methylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,
4-dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylenebis (indenyl) zirconium dichloride, methylenebis (4,5,6,7-tetrahydroindenyl) Zirconium dichloride, methylenebis (2-methylindenyl) zirconium dichloride, methylenebis (2,4-
Dimethylindenyl) zirconium dichloride, methylenebis (2-methyl-4-ethylindenyl) zirconium dichloride, methylenebis (2-methyl-4-n-
Propylindenyl) zirconium dichloride, methylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, methylenebis (2-methyl-4
-N-butylindenyl) zirconium dichloride, methylenebis (2-methyl-4-tert-butylindenyl) zirconium dichloride, methylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, ethylenebis (2-
Methylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-ethylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-n-propylinde Nil) zirconium dichloride, ethylene bis (2-methyl-4-isopropylindenyl) zirconium dichloride, ethylene bis (2-methyl-4-n-butylindenyl) zirconium dichloride, ethylene bis (2-methyl-4-ter)
t-butylindenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, propylenebis (indenyl) zirconium dichloride, methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (2- Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3-n-propylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3- Isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3-
n-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentane) Dienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-n- Propylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-isopropylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (3-n-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and the like can be mentioned.

Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified above is changed to titanium or hafnium can be used as the catalyst component (B).

The above IVB transition metal compounds are described in Japanese Patent Application Nos. 6-42282, 6-42283 and 6-568.
81 can be produced by a known method.

The solid catalyst component (C) for α-olefin polymerization used in the present invention is a linear or cyclic organic aluminum oxy compound represented by the following general formula (2) or (3).

[0045]

Embedded image

[0046]

Embedded image In the general formulas (2) and (3), R ³ and R ⁴ may be the same or different, and may be methyl, ethyl, n-propyl, isobutyl, n-butyl, isobutyl, s.
an ec-butyl group, a tert-butyl group, etc.
And 10 to 10 hydrocarbon groups. p and q are integers of 4 to 60, preferably 6 or more.

Processes for producing such compounds are known and include, for example, (a) suspension of a compound containing adsorbed water and salts containing water of crystallization (eg, copper sulfate hydrate, ammonium sulfate hydrate) in a hydrocarbon medium. A method in which a trialkylaluminum is added to a suspension to cause a reaction; (b) a method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene, or ether; (c) a method in which trimethylaluminum is mixed with triisobutyl A method in which aluminum is mixed and directly reacted with water using an appropriate organic solvent such as toluene, benzene, or ether can be exemplified.

In the present invention, it is possible to use a plurality of these organic aluminum oxy compounds in combination.

The solid olefin polymerization catalyst of the present invention comprises hollow particles (A), a group IVB transition metal compound (B), and an organoaluminum oxy compound (C). It is preferable to adopt the following method.

(1) Hollow particles (A) as a solid catalyst component
In which only the transition metal compound (B) is supported, and the solid catalyst component and the organic aluminum oxy compound (C) are supplied to the reaction system.

(2) Hollow particles (A) as a solid catalyst component
In which only the organic aluminum oxy compound (C) is supported, and the solid catalyst component and the transition metal compound (B) are supplied to the reaction system.

(3) Hollow particles (A) as a solid catalyst component
In which both the transition metal compound (B) and the organoaluminum oxy compound (C) are prepared in advance, and the solid catalyst component is supplied to the reaction system.

(4) As the solid catalyst component, the solid catalyst component of (2) is used, and the organoaluminum oxy compound (C) is supplied to the polymerization reaction system together with the solid catalyst component and the transition metal compound (B). Method.

(5) A method in which the solid catalyst component of the above (3) is used as the solid catalyst component, and the organic aluminum oxy compound (C) is supplied to the polymerization reaction system together with the solid catalyst component.

In the present invention, the hollow particles (A) may contain IVB
The following methods (a) to (c) can be employed as a method of supporting the group transition metal compound (B).

(A) A method of forming a solid catalyst by bringing a solution of a transition metal compound into contact with hollow particles.

(B) A method of forming a solid catalyst component by contacting a suspension of hollow particles dispersed in a solution of a transition metal compound with a solvent insoluble or hardly soluble in the transition metal compound.

(C) A method of forming a solid catalyst component by distilling off a solvent from a suspension of hollow particles dispersed in a solution of a transition metal compound.

The following methods (d) and (e) can be used as a method for supporting the organoaluminum oxy compound (C) on the hollow particles (A).

(D) A method of forming a solid catalyst component by contacting a suspension of hollow particles dispersed in a solution of an organic aluminum oxy compound with a solvent insoluble or hardly soluble in the organic aluminum oxy compound.

(E) A method of forming a solid catalyst component by distilling off a solvent from a suspension of hollow particles dispersed in a solution of an organoaluminum oxy compound.

As a method for supporting both the transition metal compound (B) and the organoaluminum oxy compound (C) on the hollow particles (A), the following methods (f) to (i) can be employed.

(F) By contacting a suspension of hollow particles dispersed in a solution of an organic aluminum oxy compound with a solvent insoluble or hardly soluble in the organic aluminum oxy compound, an organic aluminum oxy compound-supported carrier is formed. And then contacting the supported carrier with a solution of a transition metal compound, or distilling off a solvent from a suspension of the supported carrier dispersed in the solution of the transition metal compound to form a solid catalyst. .

(G) An organic aluminum oxy compound-supported carrier is formed by removing the solvent from the suspension of the hollow particles dispersed in the solution of the organic aluminum oxy compound, and then the carrier and the transition metal compound are mixed. A method of forming a solid catalyst by contacting a solution or distilling a solvent from a suspension of the supported carrier dispersed in a solution of a transition metal compound.

(H) A transition metal compound-supported carrier is formed by bringing a solution of a transition metal compound into contact with hollow particles, and then a suspension obtained by dispersing the carrier in a solution of an organic aluminum oxy compound and an organic solvent are mixed. A method in which a solid catalyst is formed by contacting a solvent insoluble or hardly soluble in an aluminum oxy compound, or by distilling the solvent from a suspension of the supported carrier dispersed in a solution of an organic aluminum oxy compound.

(I) After the solvent is distilled off from the suspension of the hollow particles dispersed in the solution of the transition metal compound to form a carrier supporting the transition metal compound, the carrier is converted to the organic aluminum oxy compound. The suspension dispersed in the solution is brought into contact with a solvent insoluble or hardly soluble in the organic aluminum oxy compound, or the solvent is distilled off from the suspension of the carrier dispersed in the solvent of the organic aluminum oxy compound. To form a solid catalyst component.

Examples of the soluble solvent for the transition metal compound (B) include aromatic hydrocarbons such as benzene, toluene and ethylbenzene, and halogenated hydrocarbons such as chlorobenzene and dichloroethane. Examples of the insoluble or hardly soluble solvent of the transition metal compound (B) include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane, decane, dodecane and cyclohexane.

Examples of the soluble solvent for the organic aluminum oxy compound (C) include aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene.

Examples of the solvent insoluble or hardly soluble in the organic aluminum oxy compound (C) include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane, decane, dodecane and cyclohexane.

The preparation of the above solid catalyst is usually carried out under an inert atmosphere, and the preparation temperature is arbitrary, but generally -7.
It is carried out within the range of 8 ° C to 100 ° C, preferably -78 ° C to 60 ° C. The preparation time is arbitrary, but generally 2
It is carried out within 4 hours, preferably within 12 hours.

When the solid catalyst component prepared by the above method contains the transition metal compound (B) per 100 g of hollow particles, the solid catalyst component has a transition metal atom content of 0.01 to 100 mmol,
Preferably, it contains 0.05 to 200 mmol.
When the organic aluminum oxy compound (C) is contained, 1 to 50,000 mm in terms of aluminum atoms,
Moles, preferably from 10 to 10000 mmol.

Further, when both the transition metal compound (B) and the organoaluminum oxy compound (C) are contained, the content is within the above ranges for the transition metal and aluminum, respectively. The atomic ratio (Al / M) of aluminum is in the range of 1 to 2000, preferably 5 to 1500.

The solid olefin polymerization catalyst used in the method for producing an olefin polymer of the present invention may further contain, if necessary, an organoaluminum compound represented by the following general formula (4).

[0074]

Embedded image R ⁵ _r AlX ³ _3-r (4) In the general formula (4), R ⁵ represents a hydrocarbon group having 3 to 12 carbon atoms. Preferred hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl,
Examples include an isobutyl group and a tert-butyl group. X
³ represents a halogen atom such as fluorine, chlorine or bromine or hydrogen. R is an integer of 1 to 3.

As such an organoaluminum compound,
Specifically, trialkyl aluminum such as tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tritert-butylaluminum, trioctylaluminum, alkenylaluminum such as isoprenylaluminum, di-n- Propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, ditert-butylaluminum chloride, dioctylaluminum chloride, din-propylaluminum bromide, diisopropylaluminum bromide, din-butylaluminum bromide, diisobutylaluminum Bromide, ditert-butylaluminum bromide, dioctyl Aluminum sesquichlorides such as dialkylaluminum halides such as aluminum bromide, n-propylaluminum sesquichloride, isopropylaluminum sesquichloride, n-butylaluminum sesquichloride, isobutylaluminum sesquichloride, tert-butylaluminum sesquichloride, octylaluminum sesquichloride, n -Propyl aluminum dichloride, isopropyl aluminum dichloride, n-butyl aluminum dichloride,
Isobutyl aluminum dichloride, tert-butyl aluminum dichloride, octyl aluminum dichloride, n-propyl aluminum dibromide, isopropyl aluminum dibromide, n-butyl aluminum dibromide, isobutyl aluminum dibromide, te
alkylaluminum dihalides such as rt-butylaluminum dibromide and octylaluminum dibromide, di-n-propylaluminum halide, diisopropylaluminum halide, din-butylaluminum halide, diisobutylaluminum halide, dite
Examples thereof include alkyl aluminum halides such as rt-butyl aluminum halide and dioctyl aluminum halide. Of these, trialkylaluminum is preferred. These organoaluminum compounds can be used alone or as a mixture of two or more.

The amount of the organoaluminum compound to be used is not particularly limited, but is used so that the atomic ratio (Al / M) of the organoaluminum compound to the transition metal is 10 or more, preferably 20 to 10,000. Can be

In the production method of the present invention, the olefin used for the polymerization reaction is ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,
Α-olefins such as pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or more of these can be used in combination. .

The olefin polymerization catalyst of the present invention further comprises
It is also effective for copolymerization with cyclic olefins or non-conjugated dienes. Examples of cyclic olefins include cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, and the like. Non-serving dienes include 5-ethylidene-2-norbornene,
Cyclic non-service diene such as propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- Hexadiene, 5-
Methyl-1,5-heptadiene, 6-methyl-1,5-
Heptadiene, 1,7-octadiene, 6-methyl-
The polymerization method used in the production method of the present invention includes linear non-conjugated dienes such as 1,7-octadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene and 1,9-decadiene. Either phase polymerization or gas phase polymerization is possible. In the liquid phase polymerization, an inert hydrocarbon may be used as a solvent, and furthermore, a liquefied olefin itself such as liquefied propylene and liquefied 1-butene may be used as a solvent. Benzene as a polymerization solvent,
Aromatic hydrocarbons such as toluene, ethylbenzene, xylene, butane, isobutane, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, dodecane, hexadecane, octadecane, cyclopentane, methylcyclopentane, cyclohexane, cyclopentane, Examples include alicyclic hydrocarbons such as cyclooctane, and petroleum fractions such as gasoline, kerosene, and light oil.

The concentration of the transition metal atom in the polymerization reaction system in the production method of the present invention is not particularly limited, but is preferably in the range of 10 ⁻² to 10 ⁻¹⁰ mol / l in transition metal concentration.

The pressure of the olefin in the polymerization reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² . Although the polymerization temperature is not particularly limited, it is generally in the range of -50 to 250C, preferably -30 to 100C. In the polymerization, the molecular weight can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen.

The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system. further,
The polymerization can be carried out in two or more stages by changing the reaction conditions. The olefin polymer obtained in the present invention,
It is a polymer or copolymer of an olefin alone, or a copolymer of an olefin and a conjugated or non-conjugated diene.

FIG. 1 shows the concept of preparation of the olefin polymerization catalyst according to the present invention.

[0083]

【Example】

(Example 1) <Preparation of solid catalyst (a)> 500 dried sufficiently with nitrogen
5.0 g of inorganic hollow particles (CaCO ₃ , particle diameter 500 μm, hollow inner diameter 200 μm) were put into a ml glass reactor. In another glass container, 20 ml of a toluene solution containing 30 mg of dimethylsilylbis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride and MMAO (trade name of modified methylaluminoxane (trade name, manufactured by Tosoh Akzo Co., Ltd.) Tri-tert
(Co-hydrolysate of -butylaluminum)) and 170 ml, and added dropwise to the glass reaction vessel. The obtained reaction solution was stirred at 20 ° C. for 2 hours. After standing, the supernatant was removed by a gradient method. As a result of elemental analysis, the obtained solid catalyst contained a hafnium compound at 3.6 × 10 ⁻⁶ mol / g.

<Polymerization of Propylene> 0.8 g of the above solid catalyst (a) (containing 2.9 × 10 ⁻⁶ mol of hafnium) was added to a 1.5 L stainless steel autoclave sufficiently dried with nitrogen. Liquefied propylene 1000
Then, polymerization was carried out at 60 ° C. for 1 hour. After the polymerization was completed, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. The obtained polymer was separated by filtration and dried under reduced pressure at 60 ° C. for 6 hours.

As a result, 59.7 g of polypropylene was obtained. The polymerization activity is 20.8 kg-PP / mmol-
Hf-h, the MFR of the polymer is 1.9 g / 10 min,
The bulk density was 0.35 g / ml. In addition, no polymer adhered to the polymerization vessel wall, and no fine powder passed through a standard 200-mesh sieve.

(Example 2) <Preparation of solid catalyst (b)> 500 solid dried with nitrogen
Inorganic hollow particles (Ni (OH) ₂
/ SiO ₂ , particle size 500 μm, hollow part diameter 200 μm)
5 g were charged. In another glass container, 170 ml of MMAO (manufactured by Tosoh Akzo) was added to a 20 ml toluene solution containing 30 mg of dimethylsilylbis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride.
Was added and stirred for 10 minutes. Thereafter, the mixture was dropped into the glass reaction vessel and stirred at 20 ° C. for 2 hours. After standing, the supernatant was removed by a decanting method. According to the result of elemental analysis, the obtained solid catalyst had 2.9 × 1
0 hafnium compound of ^-6 mol / g is included. <Polymerization of propylene> The solid catalyst (b) was placed in a 1.5 L stainless steel autoclave sufficiently dried with nitrogen.
1.0 g (including 2.9 × 10 ^-6 mol of hafnium)
, Then 1000 ml of liquefied propylene is added,
Polymerization was performed at 60 ° C. for 1 hour. After the polymerization was completed, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. Then, the polymer was separated by filtration and dried at 60 ° C. for 6 hours under reduced pressure.

As a result, 58.8 g of polypropylene was obtained. The polymerization activity is 20.3 kg-PP / mmol-
Hf-h, the MFR of the polymer is 2.5 g / 10 min,
The bulk density was 0.40 g / ml. In addition, no polymer adhered to the polymerization vessel wall, and no fine powder passed through a standard 200-mesh sieve.

(Comparative Example 1) <Preparation of solid catalyst (c)>
10 ml of toluene is added to a 10 ml glass reactor, and silica (particle size: 50-100 μm, baked at 600 ° C. for 8 hours)
0.7 g was suspended and brought to 0 ° C. Next, MMAO
(Tosoh Akzo Co., Ltd.) 10 m and a toluene solution containing 0.12 g of dimethylsilylbis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride were pre-contacted at 20 ° C. for 10 minutes. In addition,
Stirring was performed for 30 minutes. After completion of the reaction, toluene was distilled off at 15 ° C. under reduced pressure, and drying was performed for 4 hours in that state. According to the results of the elemental analysis, the obtained solid catalyst contained 1.0 × 1
It contained ^0-4 mol / g of a hafnium compound.

<Polymerization of Propylene> To a 1.5 L stainless steel autoclave sufficiently dried with nitrogen, 31 mg of the above solid catalyst (c) was added, and then 1000 ml of liquefied propylene was added, followed by polymerization at 60 ° C. for 1 hour. . After the polymerization was completed, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. Then, the polymer was separated by filtration and dried under reduced pressure at 60 ° C. for 6 hours.

As a result, 25.8 g of polypropylene was obtained. Polymerization activity is 8.3 kg-PP / mmol-H
fh, the MFR of the polymer was 1.6 g / 10 min, and the bulk density was 0.19 g / ml. Further, adhesion of a large amount of polymer was observed on the polymerization vessel wall, and 55 wt% of fine powder passed through a 200-mesh standard sieve.

Example 3 Preparation of solid catalyst (d) Instead of using 30 mg of dimethylsilylbis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride, 20 mg of dimethylsilylbis (2,2 The same operation as in Example 1 was carried out except that 3,5-trimethylcyclopentadienyl) zirconium dichloride was used. When the obtained solid catalyst (d) was subjected to elemental analysis, it was 1.8 × 10 ⁻⁶ mol /.
g of zirconium compound.

<Polymerization of Propylene> 0.4 g (including 7.2 × 10 ⁻⁷ mol of a zirconium compound) of the solid catalyst (d) was added to a 1.5 L stainless steel autoclave sufficiently dried with nitrogen. Next, 1000 ml of liquefied propylene was added, and polymerization was performed at 60 ° C. for 1 hour. After the polymerization, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component.
Drying under reduced pressure was performed at 60 ° C. for 6 hours.

As a result, 75.3 g of polypropylene was obtained. Polymerization activity is 105 kg-PP / mmol-Z
rh, the MFR of the polymer is 20.5 g / 10 min,
The bulk density was 0.35 g / ml. Further, no polymer adhered to the polymerization vessel wall, and no fine powder passed through a 200-mesh standard sieve was observed.

Example 4 Preparation of Solid Catalyst (e) Instead of using 30 mg of dimethylsilylbis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride, 20 mg of dimethylsilylbis (2- The same operation as in Example 1 was carried out, except that (methylindenyl) zirconium dichloride was used. When the obtained solid catalyst (e) was subjected to elemental analysis,
1.7 × 10 ⁻⁶ mol / g of the zirconium compound was contained.

<Polymerization of Propylene> 0.4 g (containing 6.8 × 10 ⁻⁷ mol of zirconium compound) of the solid catalyst (e) was added to a 1.5 L stainless steel autoclave sufficiently dried with nitrogen. Next, 1000 ml of liquefied propylene was added, and polymerization was performed at 60 ° C. for 1 hour. After the polymerization, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component.
Drying under reduced pressure was performed at 60 ° C. for 6 hours.

As a result, 85.4 g of polypropylene was obtained. Polymerization activity is 125 kg-PP / mmol-Z
rh, the MFR of the polymer is 20.5 g / 10 min,
The bulk density was 0.35 g / ml. Further, no polymer adhered to the polymerization vessel wall, and no fine powder passed through a standard 200-mesh sieve was observed.

Example 5 <Polymerization of Propylene> 1000 ml of toluene and 0.8 g of the above solid catalyst (a) (2.9 × 10 ⁻⁶ mol) were placed in a 1.5 L stainless steel autoclave sufficiently dried with nitrogen.
Was added and the temperature was raised to 60 ° C. Next, propylene was continuously introduced so that the total pressure was maintained at 7 kg / cm ^2, and polymerization was performed for 1 hour. After the polymerization was completed, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. Then, the polymer was separated by filtration and dried under reduced pressure at 60 ° C. for 6 hours.

As a result, 35.5 g of polypropylene was obtained. The polymerization activity is 12.2 kg-PP / mmol-
Hf-h, MFR of polymer is 25.2 g / 10 mi
n, bulk density was 0.32 g / ml. Further, no polymer adhered to the polymerization vessel wall, and no fine powder passed through a standard 200-mesh sieve was observed.

Example 6 <Ethylene-Propylene Copolymerization> A 1.5 m stainless steel autoclave, which had been sufficiently dried with nitrogen, was charged at 1000 m.
l of toluene and 0.8 g of the solid catalyst (a) (2.9 ×
10 ^-6 mol of hafnium compound) and add 60 ° C
The temperature rose. Next, a mixed gas of ethylene and propylene having a molar ratio of 9/91 was continuously introduced so that the total pressure was maintained at 4 kg / cm ^2, and polymerization was performed for 2 hours. After completion of the polymerization, the mixed gas was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. Then, the polymer was separated by filtration and dried at 60 ° C. for 6 hours under reduced pressure.

As a result, 22.3 g of a polyethylene propylene copolymer was obtained. Polymerization activity is 7.7 kg-
PP / mmol-Hf-h. This copolymer contained 3.5 mol% of an ethylene moiety by IR analysis. Further, there was no adhesion of the copolymer on the polymerization vessel wall,
No fine powder passed through a 0-mesh standard sieve was observed.

(Comparative Example 2) <Polymerization of Propylene> In a 1.5 L stainless steel autoclave sufficiently dried with nitrogen, 10 ml of MMAO (manufactured by Tosoh Akzo) and 1.9 mg (3.6 × 10 ^-6 m)
ol) of dimethylsilylbis (2,3,5, -trimethylcyclopentadienyl) hafnium dichloride. Next, 1 liquefied propylene
000 ml was added, and polymerization was performed at 60 ° C. for 1 hour. After the polymerization was completed, propylene was purged, and a methanol / hydrochloric acid mixture was added to decompose the catalyst component. Thereafter, the polymer was separated by filtration and dried under reduced pressure at 60 ° C. for 6 hours.

As a result, 43.7 g of polypropylene was obtained. The polymerization activity is 1.2 kg-PP / mmol-H
fh, the MFR of the polymer was 0.2 g / 10 min, and the bulk density was 0.15 g / ml. In addition, adhesion of a large amount of polymer was observed on the polymerization vessel wall, and 70% by weight of fine powder passed through a 200-mesh standard sieve.

[0103]

According to the solid olefin polymerization catalyst and the olefin polymerization method of the present invention, olefin can be polymerized with high activity, and the obtained olefin polymer has excellent powder properties without containing fine particles. It has a higher bulk specific gravity.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the concept of preparing an olefin polymerization catalyst of the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kiyoki Ito 10-2, Oibow-cho, Kanazawa-ku, Yokohama-shi, Kanagawa

Claims (5)

[Claims] An olefin polymerization catalyst comprising, as main components, the following components: (A) hollow particles; (B) a group IVB transition metal compound; and (C) an organoaluminum oxy compound. 2. The olefin polymerization catalyst according to claim 1, wherein the hollow particles are hollow spherical particles having a particle size of 1000 μm or less. 3. The olefin according to claim 1, wherein the hollow particles are hollow spherical particles composed of primary particles having a particle size of 100 μm or less and secondary particles having a particle size of 50 μm or less that bind the primary particles. Catalyst for polymerization. 4. The method according to claim 1, wherein the olefin is propylene.
4. The catalyst for olefin polymerization according to any one of claims 1 to 3. 5. A method for producing an olefin polymer, comprising polymerizing an olefin using the catalyst for olefin polymerization according to any one of claims 1 to 4.