JP3102929B2 - Solid catalyst for producing polyolefin and method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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]

2. Description of the Related Art Transition metal compounds having cyclopentadienyl group, indenyl group, fluorenyl group, or derivatives thereof as ligands, so-called metallocene compounds, are used together with a cocatalyst such as aluminoxane to polymerize an α-olefin. It is known that by doing so, a poly-α-olefin can be produced. JP-A-58-19309 discloses that (cyclopentadienyl) ₂ MeRHal (where R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, Me is a transition metal, and Ha
wherein l is a halogen), and a method of polymerizing or copolymerizing ethylene and / or an α-olefin in the presence of a catalyst comprising a transition metal compound represented by the formula: JP-A-60-35008 describes that a poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst comprising at least two kinds of metallocene compounds and an aluminoxane. JP-A-61-130314 describes a method for producing a polyolefin using a catalyst comprising a sterically fixed zircon chelate compound and an aluminoxane. The publication also discloses a method for producing a polyolefin having a high isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Are listed. JP-A-64-66
No. 124 discloses a transition metal compound having a cyclopentadienyl compound cross-linked with silicon as a ligand and a catalyst for producing a stereoregular olefin polymer containing aluminoxane as an active ingredient. JP-A-2-41303 discloses the following formula R ″ (CpR _n ) (CpR ′ _m ) MeQ _k (where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring; _n is the same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms; each R ′ _{m is the} same or different and is a hydrocarbyl residue having 1 to 20 carbon atoms; R "is a structural bridge between the Cp rings that provides steric rigidity to the catalyst; Me is 4b, 5 of the Periodic Table of the Elements.
b is a metal of group b or 6b; each Q is a hydrocarbyl residue having 1 to 20 carbon atoms or halogen;
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 good syndiotacticity can be produced by using a catalyst containing as one component. Further, the publication describes that a syndiotactic poly-α-olefin having a wide molecular weight distribution can be produced by using two or more of the above metallocene compounds.
JP-A-2-274703 discloses the following formula:

[0003]

Embedded image [Wherein, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, and R ¹ and R ² may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, carbon atom Means an alkylaryl group having 7 to 40 atoms or an arylalkenyl group having 8 to 40 carbon atoms, R ³ and R ⁴ are different, and a central atom M
R ⁵ represents a mono- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ¹

[0004]

Embedded image= BR⁶, = AlR⁶, -Ge-, -Sn-, -O-,
-S-, = SO, = SO, = NR⁶, = CO, = PR
⁶Or = P (O) R⁶, Where R⁶, R⁷You
And R⁸May be the same or different, and
, A halogen atom, an alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, number of carbon atoms
6 to 10 fluoroaryl groups, 6 to 20 carbon atoms
Aryl group, alkoxy group having 1 to 10 carbon atoms, carbon
An alkenyl group having 2 to 10 atoms and 7 to 40 carbon atoms
Arylalkyl group, aryla having 8 to 40 carbon atoms
Lucenyl group or alkyl aryl having 7 to 40 carbon atoms
Or R ⁶And R⁷Or R⁶You
And R⁸Are each formed with their attached atoms
To form a ring, and M^TwoIs silicon, germanium or
Is tin. The transition metal component represented by
Polymerization of olefins in the presence of a catalyst consisting of
And high molecular weight syndiotactic polyolefin
Are described.

Further, Japanese Patent Application Laid-Open No. 2-274704 discloses
Is a high-molecular-weight synd
A method for producing an tactic polyolefin is described.
ing. On the other hand, the so-called Kaminsky type as described above
When the active species of the catalyst is [Cp '_TwoMR) ⁺(Where Cp '= sic
Lopentadienyl derivative, M = Ti, Zr, Hf, R =
Alkyl))
Have been suggested since then, using aluminoxanes as co-catalysts.
Some catalyst systems have also been reported. Taube et al., J. O.
rganometall. Chem.,347, C9 (1988) [Cp_TwoTi
Me (THF)]⁺[BPh_Four]^-(Me = methyl group,
Ph = phenyl group)
The polymerization has been successful. Jordan et al., J. Am. Chem. Soc.,
109, 4111 (1987), [Cp_TwoZrR (L)]⁺(R
= Methyl group, benzyl group, L = Lewis base)
Shows that the ruconium complex polymerizes ethylene
You. Japanese Unexamined Patent Publication No. Hei.
No. 036 discloses cyclopentadienyl metal compounds and
Stabilizing cyclopentadienyl metal cations
Using a catalyst consisting of an ionic compound capable of
A method for polymerizing quinine is described. Zambelli et al.
Macromolecules,twenty two, 2186 (1989)
A zirconium compound having an ene derivative as a ligand;
Limethyl aluminum and fluorodimethyl aluminum
Isotactic polyp with a catalyst combining
It reports that ropylene can be produced. As above
So-called Kaminsky catalysts are generally soluble in solvents
To perform solvent polymerization or gas phase polymerization.
If the bulk density of the resulting polymer is low, poor powder properties
And problems such as adhesion of a wall to a polymerization machine have occurred. This
In order to solve these problems, Japanese Patent Application Laid-Open No.
0, JP-A-63-66206, JP-A-2-
No. 173104 discloses metallocene compounds and alkoxides.
Using a solid catalyst in which minoxane is supported on a particulate carrier
Methods for polymerizing olefins are described. But
The solid obtained using these aluminoxanes
Catalysts have the disadvantage of low activity per solid catalyst.
Was. Therefore, solid catalysts that do not use aluminoxane
Development is desired.

[0006]

The so-called Kaminsky type catalyst comprising 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, the resulting polymer has disadvantages such as low bulk specific gravity and adhesion of the polymer to a wall surface during polymerization.

[0007]

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

That is, the present invention relates to (A) (a) a tetravalent zirconia having a crosslinkable or non-crosslinkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof;
Um, from the compound and Lewis acidic compounds comprising a transition metal compound selected from compounds of titanium and hafnium (b) an organoaluminum compound (c) a solid catalyst component formed from the particulate carrier, and (B) (d) anion
Selected tetravalent zirconium, titanium and component (a)
Is to provide a compound (e) polyolefin production for a solid catalyst comprising a solid cocatalyst component formed from particulate carrier capable of stabilizing the cation of the compound fine hafnium, still present invention the (A) A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst comprising: (A) and (B); and polymerizing the olefin in the presence of a catalyst comprising: A method for producing a polyolefin.

In the present invention, in the component (A), a cross-linkable or non-cross-linkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group or a derivative thereof used as the component (a) is used. Having four valencies
Of zirconium, titanium and hafnium compounds
The exposed transition metal compound is a known compound called a so-called metallocene compound. Specific examples include the following compounds. Examples of the transition metal compound having a non-bridging ligand include cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (pentamethylcyclopentadienyl) zirconium. Examples include dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, and the like. The transition metal compound having a bridging ligand is ethylene bis. (1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9
-Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl) (9-fluorenyl) zyl
Conium dichloride, similar hafnium compounds, titanium compounds such as JP-A-1-301704, JP-A-1-319489, JP-A-2-131488, JP-A-3-9913, and JP-A-3-2160
No. 7, JP-A-3-106907, and the like.
In addition, the transition metal compound isopropylidene (cyclopentadienyl) (2,7-dit
-Butyl-9-fluorenyl) zirconium dichloride, 1,4-cyclohexanediylidenebis (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, and the like.

[0010] In the component (A) in the present invention, (b) an organoaluminum compound used as the component of the general formula _{^{R 1 j Al (OR 2)}} k H l X m ( wherein R ^1, R ² carbon R ¹ and R ² may be the same or different from each other, and X 1 represents a halogen atom, O represents an oxygen atom, H represents a hydrogen atom, and j represents 1 And k, l, and m are integers from 0 to 2 and j + k + 1 + m = 3), or a mixture thereof, and specifically, for example, trimethylaluminum, Examples thereof include triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and diisobutylaluminum hydride. Among them, triethyl aluminum,
Triisobutylaluminum is preferably used.
Component (c) and the particulate carrier used as component (e) in component (B) have an average particle diameter of 0.01 to 500.
μm, preferably in the range of 1 to 200 μm. Examples of the fine inorganic carrier include metal oxides and metal chlorides. Specifically, for example, SiO ₂ , Al ₂ O ₃ , MgCl ₂ , TiO ₂ , zeolite and the like are suitably used. Examples of the fine organic carrier include organic polymers such as polyethylene, polypropylene, polystyrene, and polynorbornene. The particulate carriers used as component (c) and component (e) may be the same or different, respectively.

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 usually used. For example, in an organic solvent, -100 ° C to 200 ° C, preferably -50 ° C.
A method in which the components (a), (b) and (c) are brought into contact at a temperature in the range of 100C to 100C is preferably used. The organic solvent used at this time is not particularly limited as long as it is inert to the metallocene compound. Specifically, aromatic solvents such as benzene, toluene, xylene, pentane, hexane, heptane, decane, and cyclohexane are used. And aliphatic and aliphatic hydrocarbons. The use ratio of the component (a) and the component (b) with respect to the component (c) is 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, respectively.
It is 0 times by weight. The solid catalyst component (A) of the present invention thus obtained has a transition metal atom of 0.01 to 5%.
0% by weight, preferably 0.05 to 20% by weight, 0.01 to 50% by weight as Al atom, preferably 0.1 to 30% by weight.
% By weight.

In the component (B) of the present invention, tetravalent zirconium and titanium are used as the component (a) used as the component ( d).
Examples of the compound capable of stabilizing the cation of the tan and hafnium compounds include a compound containing an anion capable of stabilizing the cation and a Lewis acidic compound. Examples of the anion capable of stabilizing the cation include, for example, 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 and the like. ,
Binding to the generated transition metal cation compound,
Those which strongly coordinate and do not inactivate the polymerization active species are preferably used. Examples of such suitable anions include the tetraphenylboron anion described in Taube, Jordan et al., JP-A-1-501950 and JP-A-1-5.
Examples thereof include tetrakis (pentafluorophenyl) boron anion and similar aluminum compound anion and gallium compound anion described in JP-A-02036 and JP-A-3-179006.

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. Cations can be mentioned. Examples of such a cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, and an ammonium cation. Specifically, silver cation, dicyclopentadienyl iron cation,
Triphenylcarbenium cation, triphenylphosphonium cation, tributylammonium cation and the like. The Lewis acidic compound can be used without particular limitation as long as it is a known compound exhibiting Lewis acidity and does not inactivate the polymerization active species. Preferable examples include tris (pentafluorophenyl) boron described in JP-A-3-179005.

The solid co-catalyst component (B) in the present invention can be obtained by bringing the components (d) and (e) into contact. As a method of contacting, in an organic solvent,-
A method of bringing the components (d) and (e) into contact with each other at a temperature 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, benzene, toluene, xylene, pentane, hexane, heptane, decane, aromatic and aliphatic hydrocarbons such as cyclohexane, chloroform, halogenated hydrocarbons such as dichloromethane, diethyl ether, tetrahydrofuran, In addition to ethers such as dimethoxyethane, alcohols such as methanol, ethanol, isopropanol and butanol can be exemplified. The use ratio of the component (d) to the 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 includes the component (a)
Of tetravalent zirconium, titanium and hafnium
Compounds capable of stabilizing the cation of 0.1 to
99% by weight, preferably 5 to 90% by weight.

By bringing the above-mentioned components (A) and (B) into contact, it can be used as the solid catalyst for producing a polyolefin of the present invention. The method for bringing the component (A) and the component (B) into contact is not particularly limited, and the method can be used in the polymerization of an olefin by bringing the component into contact with or without a solvent in the presence or absence of an olefin. In the polymerization of the olefin, the use ratio of the component (B) 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 a solid catalyst comprising the above components (A) and (B) in the presence of an organoaluminum compound. As the organoaluminum compound, an alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, or an alkylaluminum halide is preferably used. The polymerization method and the polymerization conditions carried out in the method of the present invention are not particularly limited, and known methods carried out in the polymerization of olefins are used, and a solvent polymerization method using an inert hydrocarbon medium, or a substantially inert hydrocarbon is used. A bulk polymerization method or a gas phase polymerization method without a medium can be used, and the polymerization is generally performed at a polymerization temperature of -100 to 200 ° C and a polymerization pressure of normal pressure to 100 kg / cm ² . Preferably -50 to 100 ° C, normal pressure to 50
kg / cm ² .

The hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention includes, for example, benzene in addition to saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane. And aromatic hydrocarbons such as toluene and xylene. The olefin used in the polymerization includes ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
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]

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 was sufficiently purged 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 0.1 mg were used.
4 g was added and the mixture was stirred at room temperature for 30 minutes. The supernatant was removed by decantation, and the solid was washed three times with 50 cm ³ of heptane to obtain a solid catalyst component (A1). As a result of analyzing this solid catalyst, 0.5 wt.
%, 7.7 wt% as Al atoms. Preparation of Solid Cocatalyst Component (B) In a 200 cm ³ glass flask sufficiently purged with nitrogen, 2.0 g of anhydrous magnesium chloride was suspended in 100 cm ³ of toluene. To this suspension was added triphenylcarbenium tetrakis (pentafluorophenyl) borate 150
mg was added and stirred at 50 ° C. for 30 minutes. The solid co-catalyst component (B) was obtained by removing the solvent under reduced pressure under high-speed stirring. As a result of analyzing this solid catalyst, it was found to contain 3.9% by weight as carbon atoms. Was charged with polymerization thoroughly the autoclave replaced with nitrogen to the prepared solid catalyst component as in the 1.5dm ³ (A1) 0.5g and solid promoter component (B) 0.3 g, liquid propylene 0.75Dm ³ In addition, polymerization was performed at 40 ° C. for 1 hour. After terminating the polymerization 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. The intrinsic viscosity (hereinafter abbreviated as [η]) of the powder measured with a tetralin solution at 135 ° C. is 0.87 dl / g, the syndiotactic pentad fraction (rrrr) measured by ¹³ C-NMR is 0.84, The bulk specific gravity was 0.33 g / cm ³ . Also, little adhesion of the polymer to the walls of the autoclave.

Example 2 The solid catalyst component (A) prepared in Example 1 was used as a polymerization catalyst.
Example 1 except that 0.5 g, 0.3 g of the solid promoter component (B) and 0.12 g of triethylaluminum were used.
Polymerization was carried out in the same manner as described above. As a result, 31.7 g of syndiotactic polypropylene powder was obtained. [Η] of the powder is 0.88 dl / g and rrrr is 0.8
6. The bulk specific gravity was 0.26 g / cm ³ , and the polymer hardly adhered to the autoclave wall.

Example 3 Synthesis of transition metal compound [isopropylidene (cyclopentadiene) (2,7-
Di-t-butyl-9-fluorene)] into a 300 cm ³ glass flask sufficiently purged with nitrogen.
12.0 g of 7-di-t-butyl-9-fluorene (Synth
sis, 335 (synthesized by the method described in 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 dropping, raise the reaction solution to room temperature,
Stir 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 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, 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 a white powder of isopropylidene (cyclopentadiene) (2,7-di-t-butyl-9-
Fluorene) was obtained. The physical properties of this compound are shown below. [Isopropylidene (cyclopentadienyl) (2,
7-di-tert-butyl-9-fluorenyl) zirconium dichloride] First, isopropylidene (cyclopentadiene) (2,7-di-tert-butyl-9-fluorene) 1 synthesized above
By lithiating 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 sufficiently purged with nitrogen. Isopropylidene (cyclopentadienyl) melted at −78 ° C. in this suspension
300 cm ³ of a solution of (2,7-di-tert-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. The 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 isopropylidene (cyclopentadienyl) (2,7-di-t-) as orange crystals. 4.3 g of (butyl-9-fluorenyl) zirconium dichloride were obtained. The physical properties of this compound are shown below. Elemental analysis _{C 29 H 34 ZrCl 2 C H} Cl calc (%) 63.97 6.25 13.0 Found (%) 64.20 6.21 12.90 Preparation isopropylidene solid catalyst component (A) Instead of (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2
7-di-t- butyl-9-fluorenyl) solid catalyst component except for using zirconium dichloride Example 1
A solid catalyst component (A2) was prepared in the same manner as in the preparation of (A1) . The obtained solid catalyst contained 0.3 wt% of Zr atoms and 7.3 wt% of Al atoms. The same procedure as in Example 1 was carried out except that the solid catalyst component (A2) obtained in Example 4 obtained as described above and the solid cocatalyst component (B) obtained in Example 1 were used as the polymerization catalyst. To perform polymerization. As a result, 29.1 g of syndiotactic polypropylene powder was obtained. [Η] of the powder was 0.70 dl / g, rrrr was 0.88, and bulk specific gravity was 0.32 g / cm ³ , and the polymer hardly adhered to the autoclave wall.

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 the powder is 0.70 dl / g, rrrr is 0.8
8. The bulk specific gravity was 0.25 g / cm ³ , and the polymer hardly adhered to the autoclave wall.

Embodiment 5Preparation of solid catalyst component (A) Silica instead of magnesium chloride (Fuji Devison
300m surface area ^Two, Average particle diameter 57μm)
Example 1 except forPreparation of solid catalyst component (A)the same as
Thus, a solid catalyst component (A3) was prepared. Got
In the solid catalyst, 0.7 wt% of Zr atoms and 9.8
It contained wt% of Al atoms.polymerization As the catalyst, the solid catalyst component (A
3) and the solid co-catalyst component (B) obtained in Example 1
Polymerization was carried out in the same manner as in Example 1 except that the polymer was used. That
Result 26.3 g of syndiotactic polypropylene powder
Powder was obtained. [Η] of the powder is 0.73 dl /
g and rrrr are 0.88 and bulk specific gravity is 0.32 g / cm.^Three
And the adhesion of the polymer to the walls of the autoclave is almost
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 the powder is 0.75 dl / g, rrrr is 0.8
9. The bulk specific gravity was 0.25 g / cm ³ , and the polymer hardly adhered to the autoclave wall.

Comparative Example 1 As a polymerization catalyst, isopropylidene (cyclopentadienyl)
(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 changed to 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, with significant polymer adhesion to the autoclave walls. Comparative Example 2 Polymerization was carried out 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. [Η] of the powder was 0.90 dl / g, rrrr was 0.84, and bulk specific gravity was 0.20 g / cm ³ , and the adhesion of the polymer to the autoclave wall was considerable.

[0026]

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

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 5-247128 (JP, A) JP 5-155926 (JP, A) JP 4-142306 (JP, A) JP 3- 234709 (JP, A) JP-A-63-22804 (JP, A) International Publication No. 92/1723 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4 / 70

Claims (3)

(57) [Claims] (A) (a) a tetravalent zirconium having a cross-linkable or non-cross-linkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof;
Um, from the compound and Lewis acidic compounds comprising a transition metal compound selected from compounds of titanium and hafnium (b) an organoaluminum compound (c) a solid catalyst component formed from the particulate carrier, and (B) (d) anion
Selected tetravalent zirconium, titanium and component (a)
A compound capable of stabilizing the cation of a compound of hafnium and hafnium . (E) A solid catalyst for producing a polyolefin comprising a solid co-catalyst component formed from a particulate carrier. 2. A method for producing a polyolefin, comprising polymerizing an olefin in the presence of the solid catalyst according to claim 1. 3. A process for producing a polyolefin, comprising polymerizing an olefin in the presence of the catalyst comprising the solid catalyst according to claim 1 and an organoaluminum compound.