JPH05125112A - Solid catalyst for polyolefin production and production of polyolefin - Google Patents

Abstract

PURPOSE:To provide the subject catalyst containing a specific transition metal compound having a ligand containing cyclopentadienyl group, etc., an organic Al compound, a solid component consisting of fine powder carrier and a cation stabilizer, etc., and having excellent powder properties. CONSTITUTION:The objective solid catalyst for the production of a polyolefin is produced by compounding (A) a solid catalyst component derived from (i) a compound of a transition metal of the group 4a to 6a of the periodic table having cross-linked or noncross-linked ligand consisting of at least one cyclopentadienyl group, indenyl group, fluorenyl group or their derivatives [e.g. isopropylidene(cyclopentadienyl) (9-fluorenyl)zirconium dichloride], (ii) an organic aluminum compound (e.g. triethylaluminum) and (iii) a fine powder carrier (e.g. anhydrous magnesium chloride) and (B) a solid cocatalyst component consisting of (iv) a compound capable of stabilizing a transition metal cation (e.g. anion of an organic boron compound) and (v) a fine powder carrier.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin, and more particularly to a method for producing a polyolefin having good particle properties by using a catalyst supported on a carrier.

[0002]

A transition metal compound having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a so-called metallocene compound, is used together with a cocatalyst such as an aluminoxane to polymerize an α-olefin. It is known that a poly-α-olefin can be produced by JP-A-58-19309 discloses (Cyclopentadienyl) ₂ MeRHal (wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, Me is a transition metal, and Ha is Ha.
1 is a halogen) and a method of polymerizing or copolymerizing ethylene and / or α-olefin in the presence of a catalyst composed of a transition metal compound represented by the formula (1) and aluminoxane. Japanese Unexamined Patent Publication (Kokai) No. 60-35008 describes that a poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst composed of at least two kinds of metallocene compounds and aluminoxane. Japanese Patent Laid-Open No. 61-130314 describes a method for producing a polyolefin using a catalyst composed of a sterically fixed zircon chelate compound and an aluminoxane. Further, the publication discloses a method for producing a polyolefin having a high degree of isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Have been described. JP-A-64-66
Japanese Unexamined Patent Publication No. 124 discloses a catalyst for producing a stereoregular olefin polymer containing a transition metal compound having a silicon-crosslinked cyclopentadienyl compound as a ligand and an aluminoxane as an active ingredient. JP-A-2-41303, there by the following formula _{R "(Cp R n) (} CpR 'm) MeQ k ( where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; each R _n may be the same or different, from 1 to 20 a hydrocarbyl residue having a carbon atom; may optionally each R _'m mother same or different, is a hydrocarbyl residue having 1 to 20 carbon atoms; R "is the structural bridge between the Cp rings that gives the catalyst steric rigidity; Me is 4b, 5 of the Periodic Table of the Elements.
a metal of group b, or 6b; each Q is a hydrocarbyl residue having from 1 to 20 carbon atoms or a halogen; 0 ≦
k ≦ 3: 0 ≦ n ≦ 4: and 1 ≦ m ≦ 4; and R ′
_m is (CpR _'m) is (CpR _n) and sterically different and is selected as the metallocene catalyst used to produce the syndiotactic polyolefin is denoted by. It is described that a poly-α-olefin having a good syndiotacticity can be produced by using a catalyst containing 1 component as a component. Further, the same publication describes that a syndiotactic poly-α-olefin having a wide molecular weight distribution can be produced by using two or more kinds of the above metallocene compounds.
JP-A-2-274703 discloses the following formula

[0003]

[Chemical 1] [In the formula, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, R ¹ and R ² may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a carbon atom. A C 7-40 alkylaryl group or a C 8-40 arylalkenyl group, wherein R ³ and R ⁴ are different and the central atom M
¹ means a mononuclear- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ^1, and R ⁵ is

[0004]

[Chemical 2]= BR⁶, = AlR⁶, -Ge-, -Sn-, -O-,
-S-, = SO, = SO, = NR⁶, = CO, = PR
⁶Or = P (O) R⁶Means R in that case⁶, R⁷Oh
And R⁸Can be the same or different from each other,
Child, halogen atom, alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, number of carbon atoms
6-10 fluoroaryl group, 6-20 carbon atoms
Aryl group, C1-C10 alkoxy group, carbon
Alkenyl group having 2 to 10 atoms, having 7 to 40 carbon atoms
Arylalkyl group, an aryl group having 8 to 40 carbon atoms
Lucenyl group or alkylaryl having 7 to 40 carbon atoms
Means a radical or R ⁶And R⁷Or R⁶Oh
And R⁸Are each made up of the atoms that they bond to
Form a ring, and M²Is silicon, germanium,
Is tin. ] The transition metal component and alumino represented by
It is possible to polymerize olefins in the presence of a catalyst consisting of xane.
And high molecular weight syndiotactic polyolefin
A method of manufacturing is described.

Further, in Japanese Patent Laid-Open No. 2-274704.
Is a high-molecular-weight syndyne using a similar hafnium compound.
A method of making tactical polyolefins is described.
ing. On the other hand, the so-called Kaminsky type as described above
The active species of the catalyst is [Cp '₂MR] ⁺(Where Cp '= Siku
Ropentadienyl derivative, M = Ti, Zr, Hf, R =
A transition metal cation represented by
Since it was suggested that aluminoxanes should not be used as co-catalysts.
Some catalytic systems have also been reported. Taube et al., J.O.
rganometall. Chem.,347, C9 (1988) [Cp₂Ti
Me (THF)]⁺[BPh_Four]^-(Me = methyl group,
Ethylene with a compound represented by Ph = phenyl group)
The polymerization is successful. Jordan et al., J. Am. Chem. Soc.,
109, 4111 (1987), [Cp₂ZrR (L)]⁺(R
= Methyl group, benzyl group, L = Lewis base)
It shows that the rukonium complex polymerizes ethylene.
It Japanese Patent Publication No. 1-501950, Japanese National Publication No. 1-502
No. 036 discloses a cyclopentadienyl metal compound and
And stabilizing cyclopentadienyl metal cations
With a catalyst composed of an ionic compound capable of producing
A method of polymerizing a tin is described. Zambelli et al.
Macromolecules,twenty two, 2186 (1989), cyclopentadiene
A zirconium compound having an ene derivative as a ligand,
Limethyl aluminum and fluorodimethyl aluminum
With a catalyst combining
It reports that ropylene can be produced. As above
So-called Kaminsky type catalysts are generally soluble in solvents
Since it is a complex system, it will not be possible to perform solvent polymerization or gas phase polymerization.
When the polymer is produced, the bulk density of the produced polymer is low and the powder properties are inferior.
However, there was a problem such as sticking to the wall of the polymerization machine. This
In order to solve these problems, JP-A-61-110861
No. 0, JP-A-63-66206, JP-A-2-
Japanese Patent No. 173104 discloses metallocene compounds and alkanes.
Using a solid catalyst in which minoxane is supported on a particulate carrier
A method for polymerizing olefins is described. But
Solids obtained using these aluminoxanes
The catalyst has the disadvantage of low activity per solid catalyst.
It was Therefore, a solid catalyst that does not use aluminoxane
Development is desired.

[0006]

The so-called Kaminsky type catalyst composed of a metallocene compound / aluminoxane as described above requires the use of a large amount of aluminoxane in order to obtain high activity. Therefore, the solid catalyst obtained from this has a problem that the activity per solid catalyst is low. Further, there are drawbacks such that the bulk specific gravity of the produced polymer is low, and the polymer adheres to the wall surface during the polymerization, so that this improvement is desired.

[0007]

Means for Solving the Problems As a result of solving the problems described above, the inventors of the present invention have earnestly studied the development of a solid catalyst for producing a polyolefin having high activity per solid catalyst and excellent powder properties, The inventors have found that the above-mentioned object can be achieved by the solid catalyst obtained without using aluminoxane, and have completed the present invention.

That is, the present invention provides (A) (a) Periodic Table 4a to 4a which has a crosslinkable or noncrosslinkable ligand composed of at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof.
Group 6a transition metal compound (b) Organoaluminum compound (c) Particulate carrier Solid catalyst component formed from (B) (d) Compound capable of stabilizing transition metal cation (e) Particulate carrier Another object of the present invention is to provide a solid catalyst for the production of polyolefin, which comprises a solid co-catalyst component formed from the above. Further, the present invention is characterized by polymerizing an olefin in the presence of the catalyst consisting of the above (A) and (B). Method for producing polyolefin, and the above (A) and (B)
The method for producing a polyolefin is characterized by polymerizing an olefin in the presence of a catalyst consisting of

In the present invention, in the component (A), at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a cross-linkable or non-crosslinkable ligand used as a derivative thereof, which is used as the component (a), is used. The transition metal compound belonging to groups 4a to 6a of the periodic table has a known compound called a so-called metallocene compound. Among them, metallocene compounds of Group 4a of the Periodic Table are preferably used. More specifically, the following compounds can be exemplified. Cyclopentadienyl zirconium trichloride as a transition metal compound having a non-bridging ligand,
Pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl)
Zirconium dichloride, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, etc. are exemplified, and the transition metal compound having a bridging ligand is ethylenebis (1-indenyl) zirconium dichloride, Ethylene bis (4,5,6,7-tetrahydro 1-
Indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (diphenylmethylene) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Similar hafnium compounds and titanium compounds, for example, JP-A-1-301704, JP-A-1-319489, JP-A-2-131488, and JP-A-3-99.
No. 13, JP-A-3-21607, and JP-A-3-21607.
Examples thereof include transition metal compounds described in Japanese Patent No. 106907. In addition, the transition metal compound isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, 1,4-cyclohexanediylidenebis (cyclopenta) Examples thereof include dienyl) (9-fluorenyl) zirconium dichloride.

In the present invention, the organoaluminum compound used as the component (b) in the component (A) is represented by the general formula R ¹ _j Al (OR ² ) _k H _l X _m (where R ¹ and R ² are carbon atoms). R ¹ and R ² may be the same or different from each other, X is a halogen atom, O is an oxygen atom, H is a hydrogen atom, and j is 1 ~ 3, k, l, m are integers from 0 to 2, j + k + l + m = 3), or a mixture thereof can be used, for example, trimethylaluminum, Examples thereof include triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, diisobutyl aluminum hydride and the like. Among them, triethyl aluminum,
Triisobutylaluminum is preferably used.
The fine particle carrier used as the component (e) in the component (c) and the component (B) has an average particle diameter of 0.01 to 500.
It is a finely divided inorganic or organic carrier in the range of μm, preferably 1 to 200 μm. Examples of the particulate inorganic carrier include metal oxides and metal chlorides. Specifically, for example, SiO ₂ , Al ₂ O ₃ , MgCl ₂ , TiO ₂ , zeolite, etc. are preferably used. Examples of the particulate organic carrier may include organic polymers such as polyethylene, polypropylene, polystyrene and polynorbornene. The particulate carriers used as the component (c) and the component (e) may be the same or different.

The solid catalyst component (A) in the present invention can be obtained by contacting the components (a), (b) and (c). The method of contacting is not particularly limited, and a method of supporting on a carrier can be used, but for example, in an organic solvent, −100 ° C. to 200 ° C., preferably −50.
A method of contacting the components (a), (b) and (c) in the range of 100 ° C to 100 ° C is preferably used. The organic solvent used in that case is not particularly limited as long as it is an inert compound with respect to the metallocene compound, but specifically, benzene, toluene, xylene, pentane, hexane, heptane, decane, cyclohexane and the like aromatic. Mention may be made of group and aliphatic hydrocarbons. The proportions of the component (a) and the component (b) used with respect to the component (c) were 0.
001 to 10 times by weight, 0.001 to 1000 times by weight, preferably 0.01 to 5 times by weight, 0.01 to 10 times by weight
It is 0 times the weight. The solid catalyst component (A) of the present invention thus obtained contains 0.01 to 5 transition metal atoms.
0% by weight, preferably 0.05 to 20% by weight, 0.01 to 50% by weight as Al atom, preferably 0.1 to 30%
Including% by weight.

In the component (B) of the present invention, the compound capable of stabilizing the transition metal cation used as the component (d) is a compound containing an anion capable of stabilizing the transition metal cation, A Lewis acidic compound can be mentioned. Examples of the anion capable of stabilizing the transition metal cation include an organic boron compound anion, an organic arsenic compound anion, an organic phosphorus compound anion, an organic aluminum compound anion, an organic gallium compound anion, etc. A substance that is high and does not bind to the produced transition metal cation compound or strongly coordinate to inactivate the polymerization active species is preferably used. Examples of such a suitable anion include, for example, the tetraphenylboron anion by Taube, Jordan, etc., as described in JP-A-1-501950, JP-A-1-502036, and JP-A-3-179006. Examples thereof include tetrakis (pentafluorophenyl) boron anion, similar aluminum compound anions, gallium compound anions, and the like.

The cation for forming an ionic compound by forming a pair with these anions is not particularly limited as long as it does not inactivate the polymerization active species, and known cations capable of forming a pair with the above anions are used. Mention may be made of cations. Examples of such cations include metal cations, organometallic cations, carbonium cations, tripium cations, ammonium cations and the like. Specifically, silver cation, dicyclopentadienyl iron cation,
Examples thereof include triphenylcarbenium cation, triphenylphosphonium cation, tributylammonium cation, and the like. The Lewis acidic compound is a known compound exhibiting Lewis acidic property and can be used without particular limitation as long as it does not inactivate the polymerization active species. Preferred examples include tris (pentafluorophenyl) boron described in JP-A-3-179005.

The solid cocatalyst component (B) in the present invention can be obtained by bringing the above-mentioned components (d) and (e) into contact with each other. As a method of contacting, in an organic solvent,
A method of contacting the components (d) and (e) in the range of 100 ° C to 300 ° C, preferably -50 ° C to 200 ° C is preferably used. As the organic solvent used at that time,
Although not particularly limited, specifically, aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, pentane, hexane, heptane, decane and cyclohexane, halogenated hydrocarbons such as chloroform and dichloromethane, diethyl ether, tetrahydrofuran, In addition to ethers such as dimethoxyethane, alcohols such as methanol, ethanol, isopropanol, butanol and the like can be mentioned. The proportion of component (d) used with respect to component (e) is 0.001 to 100 times by weight, preferably 0.01 to 50 times by weight. The solid catalyst component (B) of the present invention thus obtained contains 0.1 to 99 compounds capable of stabilizing the transition metal cation.
%, Preferably 5 to 90% by weight.

By contacting the above-mentioned components (A) and (B), they can be used as the solid catalyst for producing the polyolefin of the present invention. The method of contacting the component (A) and the component (B) is not particularly limited, and the component (A) and the component (B) can be used for polymerization of an olefin by contacting in the presence or absence of the olefin in a solvent or without a solvent. In the polymerization of olefin, the ratio of the component (B) used to the component (A) is 0.01 to 50 times by weight, preferably 0.1 to 10 times by weight.

Further, in the present invention, a polyolefin can be produced by using the solid catalyst comprising the above components (A) and (B) in the presence of an organoaluminum compound. As the organic aluminum compound, alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride or alkylaluminum halide is preferably used. There are no particular restrictions on the polymerization method and polymerization conditions used in the method of the present invention, and known methods used in the polymerization of olefins can be used, including solvent polymerization methods using an inert hydrocarbon medium, or substantially inert hydrocarbons. A bulk polymerization method or a gas phase polymerization method in which no medium is present can also be used, and the polymerization temperature is generally -100 to 200 ° C., and the polymerization pressure is generally atmospheric pressure to 100 kg / cm ² . Preferably -50 to 100 ° C, normal pressure to 50
It is kg / cm ² .

Examples of the hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, and benzene. Aromatic hydrocarbons such as, toluene, xylene, etc. can also be used. As the olefin used in the polymerization, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Examples thereof include olefins having 2 to 25 carbon atoms such as tetradecene, 1-hexadecene and 1-octadecene. In the present invention, it can be used not only for homopolymerization of olefins but also for producing copolymers of olefins having about 2 to 25 carbon atoms such as propylene and ethylene, propylene and 1-butene.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Preparation of solid catalyst component (A) 2.0 g of anhydrous magnesium chloride was suspended in 100 cm ³ of heptane in a 200 cm ³ glass flask which had been sufficiently replaced with nitrogen. To this suspension, 100 mg of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride synthesized by the method described in JP-A-2-41303 and triethylaluminum.
4 g was added and stirred at room temperature for 30 minutes. The supernatant liquid was removed by decantation, and the solid catalyst component (A1) was obtained by washing with 50 cm ³ of heptane three times. As a result of analyzing this solid catalyst, 0.5 wt% as Zr atom
%, And 7.7 wt% as Al atom. Preparation of Solid Cocatalyst Component (B) 2.0 g of anhydrous magnesium chloride was suspended in 100 cm ³ of toluene in a 200 cm ³ glass flask that had been sufficiently replaced with nitrogen. To this suspension is added triphenylcarbenium tetrakis (pentafluorophenyl) borate 150
mg was added, and the mixture was stirred at 50 ° C. for 30 minutes. The solid promoter component (B) was obtained by removing the solvent under reduced pressure under high-speed stirring. As a result of analysis of this solid catalyst, it was found to contain 3.9 wt% as carbon atoms. Polymerization 0.5 g of the solid catalyst component (A1) and 0.3 g of the solid co-catalyst component (B) prepared as described above were charged into a 1.5 dm ³ autoclave which had been sufficiently replaced with nitrogen, and 0.75 dm ³ of liquid propylene was added. In addition, polymerization was carried out at 40 ° C. for 1 hour. After the polymerization was stopped by adding a small amount of methanol to the system, unreacted propylene was purged and dried to obtain 18.4 g of syndiotactic polypropylene powder. Intrinsic viscosity (hereinafter abbreviated as [η]) measured with a tetralin solution of powder at 135 ° C. is 0.87 dl / g, syndiotactic pentad fraction (rrrr) measured with ¹³ C-NMR is 0.84, The bulk specific gravity was 0.33 g / cm ³ . Further, there was almost no adhesion of the polymer to the wall of the autoclave.

Example 2 As a polymerization catalyst, the solid catalyst component (A) prepared in Example 1
Example 1 except that 0.5 g, solid promoter component (B) 0.3 g and triethylaluminum 0.12 g were used.
Polymerization was carried out in the same manner as in. As a result, 31.7 g of syndiotactic polypropylene powder was obtained. The powder [η] is 0.88 dl / g and rrrr is 0.8
6. The bulk specific gravity was 0.26 g / cm ³ , and there was almost no adhesion of the polymer to the wall of the autoclave.

Example 3 Synthesis of transition metal compound [isopropylidene (cyclopentadiene) (2,7-
Di-t-butyl-9-fluorene)] In a 300 cm ³ glass flask with sufficient nitrogen substitution,
12.0 g of 7-di-t-butyl-9-fluorene (Synth
sis, 335 (1984)) was dissolved in 100 cm ³ of tetrahydrofuran. To this solution, 44 mmol of a methyllithium ether solution was added dropwise at -78 ° C. After completion of dropping, raise the reaction solution to room temperature,
The mixture was stirred at the same temperature for 3 hours. To this reaction solution, 4.6 g of 6,6-dimethylfulvene diluted with 50 cm ³ of tetrahydrofuran was added dropwise at -78 ° C. After finishing the dropping
The reaction temperature was raised to room temperature and stirring was continued for another 10 hours. The reaction was stopped by adding 100 cm ^{3 of} 3.6% hydrochloric acid water, and the ether layer was washed with water and evaporated to dryness to obtain a reddish brown viscous liquid. The viscous liquid was recrystallized from hot acetone to give white powder of isopropylidene (cyclopentadiene) (2,7-di-t-butyl-9-
Fluorene) 12.2g was obtained. The physical properties of this compound are shown below. [Isopropylidene (cyclopentadienyl) (2,
7-Dit-butyl-9-fluorenyl) zirconium dichloride] First, the isopropylidene (cyclopentadiene) (2,7-dit-butyl-9-fluorene) 1 synthesized above.
By lithiation of 0.0 g with n-butyllithium, isopropylidene (cyclopentadiene) (2,
A dilithium salt of 7-di-t-butyl-9-fluorene) was prepared. Next, 6.1 g of zirconium tetrachloride was suspended in 100 cm ³ of methylene chloride in a 500 cm ³ glass flask which had been sufficiently replaced with nitrogen. Isopropylidene (cyclopentadienyl) melted in this suspension at -78 ° C
300 cm ³ of a solution of (2,7-di-t-butyl-9-fluorenyl) dilithium in methylene chloride was added at −78 ° C. After stirring at −78 ° C. for 4 hours, the temperature was slowly raised to room temperature, and the reaction was continued at that temperature for another 15 hours. A reddish brown solution containing a white precipitate of lithium chloride was filtered off, and the filtrate was concentrated and then cooled at -30 ° C for 24 hours to give orange crystals of isopropylidene (cyclopentadienyl) (2,7-di-t- 4.3 g of butyl-9-fluorenyl) zirconium dichloride were obtained. The physical properties of this compound are shown below. Elemental analysis value C ₂₉ H ₃₄ ZrCl ₂ CH Cl calculated value (%) 63.97 6.25 13.0 measured value (%) 64.20 6.21 12.90 Preparation of solid catalyst component (A) Isopropylidene Instead of (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, the isopropylidene (cyclopentadienyl) (2,
Solid catalyst component of Example 1 except that 7-di-t-butyl-9-fluorenyl) zirconium dichloride was used.
The solid catalyst component (A2) was prepared in the same manner as the preparation of (A1) . The obtained solid catalyst contained 0.3 wt% Zr atoms and 7.3 wt% Al atoms. In the same manner as in Example 1 except that the solid catalyst component (A2) obtained in Example 4) obtained as described above and the solid promoter component (B) obtained in Example 1 were used as the polymerization catalyst. Polymerization was carried out. As a result, 29.1 g of syndiotactic polypropylene powder was obtained. The powder [η] was 0.70 dl / g, rrrr was 0.88, and the bulk specific gravity was 0.32 g / cm ³ , and there was almost no adhesion of the polymer to the wall of the autoclave.

Example 4 The solid catalyst component (A2) obtained in Example 3 as a polymerization catalyst,
Polymerization was carried out in the same manner as in Example 1 except that the solid promoter component (B) obtained in Example 1 and 0.12 g of triethylaluminum were used. As a result, 52.9 g of syndiotactic polypropylene powder was obtained. [Η] of powder is 0.70 dl / g, rrrr is 0.8
8. The bulk specific gravity was 0.25 g / cm ³ , and there was almost no adhesion of the polymer to the wall of the autoclave.

Example 5Preparation of solid catalyst component (A) Silica instead of magnesium chloride (Fuji Davison
Company, surface area 300m ², Average particle size 57 μm)
Of Example 1 except thatPreparation of solid catalyst component (A)same as
Then, the solid catalyst component (A3) was prepared. Got
0.7 wt% Zr atoms and 9.8 in the solid catalyst.
It contained wt% of Al atoms.polymerization As the catalyst, the solid catalyst component (A
3) and the solid promoter component (B) obtained in Example 1
Polymerization was performed in the same manner as in Example 1 except that it was used. That
Results 26.3 g of syndiotactic polypropylene powder
Uder was obtained. [Η] of powder is 0.73dl /
g, rrrr is 0.88, bulk specific gravity is 0.32 g / cm³
And the adhesion of polymer to the autoclave wall is
I didn't.

Example 6 The solid catalyst component (A3) obtained in Example 5 as a polymerization catalyst,
Polymerization was carried out in the same manner as in Example 1 except that the solid promoter component (B) obtained in Example 1 and 0.12 g of triethylaluminum were used. As a result, 54.5 g of syndiotactic polypropylene powder was obtained. [Η] of powder is 0.75 dl / g, rrrr is 0.8
9. The bulk specific gravity was 0.25 g / cm ³ , and almost no polymer was attached to the wall of the autoclave.

Comparative Example 1 Isopropylidene (cyclopentadienyl) as a polymerization catalyst
(9-fluorenyl) zirconium dichloride 1 mg,
Polymerization was carried out in the same manner as in Example 1 except that 0.05 g of triethylaluminum and the solid promoter component (B) obtained in Example 1 were used and the polymerization time was 15 minutes. As a result, 55.1 g of syndiotactic polypropylene powder was obtained. [Η] of powder is 0.86dl
/ G, rrrr is 0.82, bulk specific gravity is 0.12 g / cm
³ and there was considerable polymer adhesion to the walls of the autoclave. Comparative Example 2 Polymerization was performed in the same manner as in Example 1 except that the solid catalyst component (A1) obtained in Example 1 and 100 mg of triphenylcarbenium tetrakis (pentafluorophenyl) borate were used as the polymerization catalyst. As a result, 18.4 g of syndiotactic polypropylene powder was obtained. The powder [η] was 0.90 dl / g, rrrr was 0.84, and the bulk specific gravity was 0.20 g / cm ³ , and the adhesion of the polymer to the wall of the autoclave was considerable.

[0026]

EFFECTS OF THE INVENTION By using the solid catalyst of the present invention and carrying out the method of the present invention, a polyolefin having a good powder property can be produced, and adhesion of the polymer to the wall of the polymerization machine is prevented. Can be industrially extremely valuable.

Claims (3)

[Claims] 1. Periodic Table 4a to (a) (a) having a bridged or non-bridged ligand composed of at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof.
Group 6a transition metal compound (b) Organoaluminum compound (c) Particulate carrier Solid catalyst component formed from (B) (d) Compound capable of stabilizing transition metal cation (e) Particulate carrier A solid catalyst for producing a polyolefin comprising a solid co-catalyst component formed from. 2. A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of the solid catalyst according to claim 1. 3. A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of the solid catalyst according to claim 1 and a catalyst comprising an organoaluminum compound.