JPH06145239A - Catalyst for alpha-olefin polymerization and production of alpha-olefin polymer using the same - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst excellent in catalytic activity duration and storage stability and capable of providing a polymer having good particle properties in high yield by impregnating almoxane, etc., into a specific organic porous polymer and preliminarily polymerizing an olefin with the resultant impregnated solid. CONSTITUTION:The objective catalyst is obtained by impregnating (B1) almoxane and (A1) a transition metal compound of the group IVB to VIB of the periodic table having one or more conjugated five membered ring ligands [e.g. bis(cyclopentadienyl)zirconium dichloride] into (A2) an organic porous polymer having >=0.3cc/g sum of pore volume of total pores having 5-1000mum average particle diameter and 0.006-10mum pore diameter and >=50% ratio of sum of pore volume of total pores having 0.05-2mum pore diameter to the sum of pore volume of total pores having 0.006-10mum pore diameter and then bringing the resultant impregnated solid into contact with (C1) an olefin under vapor phase conditions to preliminarily polymerize the olefin. Furthermore, the catalyst is brought into contact with (D) alpha-olefin to provide the objective alpha-olefin polymer.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a process for producing an olefin polymer using the same. More specifically, the present invention is a catalyst for olefin polymerization which is highly active when applied to the polymerization of olefins and enables the production of a polymer having good particle properties, and an olefin polymer comprising the same. It relates to the manufacturing method.

[0002]

2. Description of the Related Art In recent years, a highly active catalyst for olefin polymerization by combining a zirconocene compound and alumoxane has been proposed (Japanese Patent Laid-Open Nos. 58-19309 and 60-35007). Further, there is a proposal that enables the production of various stereoregular polymers by designing the structure of the ligand (Japanese Patent Laid-Open No. 61-130314).
No. 63-295607, JP-A-1-301704.
And Nos. 2-41303). Although these proposals can produce a polymer having high activity and a narrow molecular weight distribution, on the other hand, the catalyst has a very small particle size (usually about 1 to 50 μm) because the catalyst is soluble in the solvent toluene. However, it was difficult to industrially produce a polymer with high efficiency. In addition, this method requires a large amount of alumoxane, resulting in high cost. Various proposals have been made to solve such problems. In JP-A-64-51408, JP-A-1-275609 and JP-A-3-140305, the alumoxane and the metallocene compound are preliminarily contacted with each other to form the polymer particles. However, particles can be formed by this method only in so-called liquid-phase bulk polymerization using a propylene solvent, and a polymer having a controlled particle size cannot be obtained by slurry polymerization or gas-phase polymerization using an inert solvent.

Japanese Patent Laid-Open Nos. 61-296008 and 63-5.
1407, 63-152608 and WO88-
Japanese Patent No. 05058 proposes a catalyst in which a catalyst component is supported on an inorganic oxide, particularly silica. These technologies have enabled the production of granular polymers even in the case of gas phase polymerization, but the activity per supported catalyst is low due to the limited catalyst components supported on silica, and unnecessary in the polymer. Since such silica remains, it is not preferable because it causes deterioration of polymer quality, such as deterioration of moldability, surface roughness, and fish eyes.

On the other hand, JP-A-63-92621 and W
In each of O88-05058 publications, it is proposed to support a catalyst component on polyethylene particles. According to this method, it is possible to prevent the deterioration of the quality of the product polymer due to the inorganic oxide used as the carrier, but the catalyst component is less likely to be supported than the inorganic oxide, and the activity is low and the supporting is insufficient. Since the catalyst component is desorbed during the polymerization to produce a large amount of fine particles, the object of particle formation has not been sufficiently achieved. Further, in these proposals, only the production of an ethylene-based polymer, which is relatively active, is carried out, and the development of a particle-forming technique that enables the production of polypropylene is desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and even when it is applied to slurry polymerization or gas phase polymerization, the particle property of We provide an olefin polymerization catalyst that is highly active and can be produced without using a large amount of alumoxane compounds, even with excellent polymers, especially polypropylene, which was difficult in the prior art. It is intended to provide a method for producing a coalescence.

[0006]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present invention has been found as a result of intensive studies on the above objects. That is, the solid catalyst for α-olefin polymerization according to the present invention is obtained by impregnating the following component (i) with the component (ii) and the component (iii), and then contacting this with an olefin under a gas phase condition for polymerization. That is obtained by subjecting to pre-polymerization consisting of
It is characterized by. Component (i): an organic porous polymer having an average particle size of 5 to 1000 μm and a pore size of 0.006 to 10 μm
The total pore volume of all pores is 0.3 cc / g or more, and the total pore volume of all pores having a pore diameter of 0.05 to 2 μm is 0.006 to 50% or more of the total pore volume of all pores having a size of 10 μm, component (ii); alumoxane, component (iii); periodic table IVB to VIB having at least one conjugated five-membered ring ligand Group transition metal compounds.

Further, the method for producing an α-olefin polymer according to the present invention comprises the above solid catalyst for α-olefin polymerization,
It is characterized in that an α-olefin is brought into contact with each other and polymerized. Another method for producing an α-olefin polymer according to the present invention is characterized in that an α-olefin is brought into contact with a catalyst composed of the solid catalyst for α-olefin polymerization and an organoaluminum compound to polymerize, To do.

<Effect> According to the present invention, a polymer having a small ash component such as an inorganic oxide, particularly a propylene-based polymer which has been difficult to obtain in the past, can be obtained in a high yield with a good particle shape. It is also possible, and the activity durability and storage stability of the catalyst are improved. It is understood that such an effect is completely unpredictable from the related art.

[Detailed Description of the Invention] [Solid Catalyst for α-Olefin Polymerization] The α-olefin polymerization catalyst according to the present invention comprises a component (i) impregnated with a component (ii) and a component (iii), Then, it was obtained by subjecting it to prepolymerization which comprises contacting an olefin under gas phase conditions to polymerize. Here, "component (i)
"The one obtained by impregnating the component (ii) and the component (iii) therein" refers to a substance obtained by impregnating the component (i) with only the component (ii) and the component (iii). , The component (i
Including those obtained by impregnating other components than i) and component (iii).

<Component (i)> The component (i) is an organic porous polymer having an average particle size of 5 to 1000 μm, preferably 10 to 700 μm, more preferably 20 to 500 μm, and having a pore size of 0. The total pore volume of all pores of 0.006 to 10 μm is 0.3 cc / g or more, preferably 0.8 cc / g or more, more preferably 1.0 cc / g or more, and the pore size is 0. The total pore volume of all pores having a diameter of 0.005 to 2 μm is 0.006 to 10 μm.
Is 50% or more, preferably 60% or more of the total pore volume of all pores. This component (i) is
If the total pore volume of all pores having a pore diameter of 0.006 to 10 μm is less than 0.3 cc / g, the amount of catalyst component that can be impregnated in component (i) is low, and It is impossible to obtain sufficient activity. Impregnation with a catalyst component, especially alumoxane, is difficult for pores with a diameter of less than 0.05 μm, and if there are many pores with a diameter of more than 2 μm, the catalyst component desorbs from the carrier particles during polymerization and polymerization is initiated or continued. Therefore, it is not preferable because it causes formation of fine particle polymer. Here, the pore volume and the pore diameter are measured using a porosimeter (“Poresizer 9310 type” manufactured by Micromeritex Co., Ltd.), and the average particle size of the polymer is “Spica II” image analyzer manufactured by Nippon Avionics Co., Ltd. The number average particle size distribution is obtained by microscopic observation using, and the number average particle size distribution is converted into a weight average particle size distribution.
That is, it means D ₅₀ .

The kind of the organic porous polymer having the above characteristics is arbitrary as long as the above conditions are satisfied. Generally, (a) polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer Polymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, propylene-
Α-olefin polymers such as divinylbenzene copolymer,
(B) Polystyrene, aromatic unsaturated hydrocarbon polymers such as styrene-divinylbenzene copolymer, and (c) polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene ether, polyethylene Terephthalate,
Examples thereof include polar group-containing polymers such as polycarbonate. Among these, α-olefin polymers and aromatic unsaturated compound polymers are preferable because of less side reaction with the catalyst component, and more preferable are α-olefin polymers of the same type as the target polymer. .

<Component (ii)> The component (ii) is alumoxane. Alumoxane is a product obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane obtained from one type of trialkylaluminum,
Examples thereof include isobutylalumoxane and the like, and methylethylalumoxane, methylbutylalumoxane, methylisobutylalumoxane and the like obtained from two types of trialkylaluminums and water.

In the present invention, it is possible to use a plurality of these alumoxanes in combination, and it is also possible to use alumoxane in combination with other alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. Is. Further, it is also possible to use a modified alumoxane by reacting two kinds of alumoxane or one kind of alumoxane with another organoaluminum compound. Preferred among these are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane and mixtures of these alumoxanes and trialkylaluminums. Particularly preferred is
Methylalumoxane and methylisobutylalumoxane. Of these, ²⁷ are particularly suitable for the polymerization of propylene.
Chemical shift in Al-NMR measurement is 160-25
Methylisobutylalumoxane, which is characterized by having a line width of 3000 Hz or more, located between 0 ppm is preferable.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether, (b) a salt hydrate having a trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. Method of reacting with hydrate, (c) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (d) Mixing trimethylaluminum and triisobutylaluminum, and mixing with toluene, benzene, ether, etc. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum and heating and reacting with a salt hydrate having water of crystallization, for example, copper sulfate, aluminum sulfate hydrate, ( F) Impregnate silica gel with water and treat with triisobutylaluminum. After, adding treated with trimethylaluminum, method (g) synthesized in methylalumoxane and isobutyl alumoxane known methods, these two components are mixed predetermined amounts, reacted under heating.

<Component (iii)> The component (iii) is a group IVB to VIB transition metal compound of the periodic table having at least one conjugated five-membered ring ligand. Specifically, the following general formula (1): Q _a (C ₅ H _5-ab R ¹ _b ) (C ₅ H _5-ac R ² _c ) MeXY (1) or the following general formula (2): S There is a transition metal compound represented by _a (C ₅ H _5-ad R ³ _d ) ZMeXY (2).

Here, Q represents a bonding group bridging the two conjugated five-membered ring ligands, and S represents a bonding group bridging the conjugated five-membered ring ligand and the Z group. Specifically, (i) alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group; (b) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene. Group, disilylene group,
A silylene group such as a tetramethyldisilylene group; (C) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [specifically (CH ₃ ) ₂ G
e group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆
H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group,
_(CH 3) B _group, (C _{4 H} 9) B _group, (C _{6 H} 5) B
Group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group, etc.] and the like. Preferred are alkylene groups and silylene groups. a is 0 or 1. In the above general formula, (C ₅ H _5-ab R ¹ _b ), (C ₅
H _5-ac R ² _c ) and (C ₅ H _5-ad R ³ _d ) are the conjugated five-membered ring ligands, which are defined separately, but are not limited to b, c and d, and R ^Since the definitions themselves of ¹ , R ² and R ³ are the same (detailed later),
It goes without saying that the three conjugated five-membered ring groups may be the same or different.

One specific example of this conjugated five-membered ring group is b =
0 (or c = 0, d = 0) cyclopentadienyl group (no substituent other than the bridging group Q or S).
This conjugated five-membered ring group is b ≠ 0 (or c ≠ 0, d ≠ 0)
And one having a substituent, one specific example of R ¹ (or R ₂ , R ³ ) is a hydrocarbon group (C _1- ).
C _20, preferably a C ₁ -C _12), the hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and two of which are when it is present a plurality May be bonded at the other end to form a ring with a part of the cyclopentadienyl group. A typical example of the latter is R ¹
(Or R ² , R ³ ) share a double bond of the cyclopentadienyl group to form a condensed 6-membered ring,
That is, the conjugated 5-membered ring group is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated 5-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ¹ , R ² and R ³ are, in addition to the above C _{1 to} C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon groups, halogen groups (for example, fluorine, chlorine and bromine), Alkoxy groups (for example, those of C _{1 to} C ₁₂ ), silicon-containing hydrocarbon groups (for example, silicon atom to -Si (R))
(R ′) (R ″) in the form of a group having about 1 to 24 carbon atoms, and a phosphorus-containing hydrocarbon group (for example, a phosphorus atom is —P
(A group having about 1 to 18 carbon atoms in the form of (R) (R ')),
A nitrogen-containing hydrocarbon group (for example, a nitrogen atom is -N (R)
(R ') group containing about 1 to 18 carbon atoms or a boron-containing hydrocarbon group (for example, a boron atom containing -B).
(R) is a group having about 1 to 18 carbon atoms in the form of (R '). When b (or c, d) is 2 or more and R ¹ (or R ² , R ³ ) is present in plural, they may be the same or different. b, c and d are 0 ≦ b ≦ 5, 0 ≦ c ≦ 5 and 0 ≦ d ≦ 5 when a is 0,
Is 1 is an integer that satisfies 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4. Me is a transition metal of Group IVB to VIB of the Periodic Table, preferably titanium, zirconium and hafnium. Zirconium is particularly preferable.

Z is oxygen (-O-), sulfur (-S-),
An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group having 1 to 40 carbon atoms, preferably 1 to 1
8 is a phosphorus-containing hydrocarbon group. When a = 1, part of the Z group is bonded to the S group which is a bonding group.

X and Y are each hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms, and a carbon number. 1 to 20, preferably 1 to 12 phosphorus-containing hydrocarbon group (specifically, for example, diphenylphosphine group), or 1 to 20 carbon atoms, preferably 1 to 12
Is a silicon-containing hydrocarbon group (specifically, for example, a trimethylsilyl group or a bis (trimethylsilyl) methyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferable. Specific examples of this transition metal compound when Me is zirconium are as follows.

(A) A transition metal having no conjugated cross-linking group and two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclopenta). (Dienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (4) 6) Bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) Bis (n-butylcyclopentadienyl) zirconium dichloride, (8) Bis (indenyl) zirconium dichloride, (9) Bis (fluorenyl) zirconium dichloride, (10) Bis (cyclopentadienyl)
Zirconium monochloride monohydride,

(11) Bis (cyclopentadienyl) methylzirconium monochloride, (12) Bis (cyclopentadienyl) ethylzirconium monochloride, (13)
Bis (cyclopentadienyl) phenyl zirconium monochloride, (14) Bis (cyclopentadienyl) zirconium dimethyl, (15) Bis (cyclopentadienyl) zirconium diphenyl, (16) Bis (cyclopentadienyl) zirconium diphenyl Neopentyl, (17) bis (cyclopentadienyl) zirconium dihydride, (18) (cyclopentadienyl) (indenyl) zirconium dichloride, (19) (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(B) a transition metal compound having two five-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride, (3) Ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride,
(5) ethylenebis (indenyl) zirconium monomethoxymonochloride, (6) ethylenebis (indenyl) zirconium diethoxide, (7) ethylenebis (indenyl) zirconium dimethyl, (8) ethylenebis (4,5,6,6) 7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride,

(11) ethylenebis (2,4-dimethylindenyl) zirconium dichloride, (12) ethylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-Dimethylcyclopentadienyl) zirconium dichloride, (13) ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5'-
Methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (15) isopropylidene Bis (indenyl) zirconium dichloride, (16) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (17) isopropylidene (2-methyl-4) -Tert-butylcyclopentadienyl) (3'-tertbutyl-5-methylcyclopentadienyl) zirconium dichloride, (18) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (19) Methylene (cyclopentadienyl) (3,4-dimme Le cyclopentadienyl) zirconium dichloride hydride, (20)
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl,

(21) Methylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium diphenyl, (22) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (23) methylene (cyclopentadienyl)
(Tetramethylcyclopentadienyl) zirconium dichloride, (24) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (25) isopropylidene (cyclopentadienyl) (2, 3,4,5-Tetramethylcyclopentadienyl) zirconium dichloride, (26) Isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (27) Isopropylidene (cyclopentadienyl) (fluorenyl) ) Zirconium dichloride, (28) isopropylidene (2-
Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (29) isopropylidene (2,5-
Dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (30)
Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride,

(31) Ethylene (cyclopentadienyl)
(3,5-dimethylcyclopentadienyl) zirconium dichloride, (32) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (33)
Ethylene (2,5-dimethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (34) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (35) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium Dichloride, (36)
Diphenylmethylene (cyclopentadienyl) (3
4-diethylcyclopentadienyl) zirconium dichloride, (37) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (38)
Cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethyldimethylcyclopentadienyl) zirconium dichloride and the like.

(C) a transition metal compound having a silylene group-bridged five-membered ring ligand, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,5)
6,7-Tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylene bis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) zirconium dichloride, (5) phenylmethylsilylenebis (indenyl) zirconium dichloride, (6) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (7) ) Phenylmethylsilylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) zirconium dichloride, (8) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2,4,5-trimethylcyclopentadienyl) zirconium dichloride, (9) phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (10) diphenylsilylenebis (indenyl) zirconium dichloride,

(11) Tetramethyldisilirenebis (indenyl) zirconium dichloride, (12) Tetramethyldisilirenebis (cyclopentadienyl) zirconium dichloride, (13) Tetramethyldisilirene (3-methylcyclopentadienyl) (Indenyl) zirconium dichloride, (14) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (15) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium Dichloride, (16) Dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (17) Dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride Lido, (18)
Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (1
9) Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (20) Dimethylsilylene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride,

(21) Dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (22) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium Dichloride, (23) Dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (24) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (25) Dimethylsilylene ( 2-Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (26) Dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (27) Diethylsilylene (2-methylcyclopentadienyl) (2,7-di- - butyl fluorenyl) zirconium dichloride, (28) dimethylsilylene (2,5-dimethyl-cyclopentadienyl) (2,
7-di-t-butylfluorenyl) zirconium dichloride, (29) dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Zirconium dichloride, (30) dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride,

(31) Dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (32) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (33) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (34) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride and the like.

(D) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, for example (1) dimethylgermanium bis (indenyl) zirconium dichloride, ( 2) Dimethyl germanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) Methylaluminum bis (indenyl)
Zirconium dichloride, (4) phenylaluminum bis (indenyl) zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride, (6) ethylforanobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride, etc. are exemplified.

(E) Transition metal compounds having one five-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride, (2) indenyl-bis (phenyl) aminozirconium Dichloride,
(3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4)
Pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) dimethylsilylene (tetramethylcyclopentadienyl) phenylaminozirconium dichloride, (6) dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, (7)
Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride,
(8) Dimethylgermane (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride,
Etc. are illustrated. (F) Further, it is also possible to use the compounds of the above (a) to (e) in which chlorine is replaced with bromine, iodine, hydride, methyl, phenyl or the like.

Further, in the present invention, the central metal of the zirconium compound exemplified in the above (a) to (f) as the component (iii) is zirconium to titanium, hafnium, niobium,
A compound replacing molybdenum or tungsten can also be used. Among these, zirconium compounds, hafnium compounds and titanium compounds are preferable. More preferred are zirconium compounds and hafnium compounds crosslinked with alkylene groups or silylene groups.

<Preparation of Solid Catalyst> The solid catalyst of the present invention comprises
It was obtained by preliminarily polymerizing by impregnating component (i) with component (ii) and component (iii) and then contacting it with an olefin under gas phase conditions for polymerization. The method of impregnating the component (ii) and the component (iii) in the component (i) is arbitrary, but in general, the component (ii) and the component (iii) are dissolved in an inert solvent in which they can be dissolved. A method of dissolving and mixing with component (i), and then distilling off the solvent under reduced pressure or in an inert gas stream, (b) component (ii) and component (iii) are dissolved in an inert solvent, and then solid Is concentrated within a range that does not precipitate, and then the component (i) is added in such an amount that the total amount of the concentrated solution obtained above can be retained in the particles, and (c) the solution of the component (ii) and the component (iii) are sequentially added. The method of specifically impregnating the component (i) and the like are exemplified.

Component (ii) and component (iii) of the present invention are
Since it is generally a solid, this impregnation operation requires an inert solvent for solubilizing the components (ii) and (iii). Examples of the inert solvent include benzene, toluene, xylene, hexane, heptane, octane, decalin, dichloromethane, dichloroethane, chloropropane and chlorobenzene. The remaining amount of the inert solvent in the impregnated state is arbitrary and varies depending on the pore volume of the organic porous polymer (component (i)) used, but is generally 0 to the impregnated organic porous polymer. 70% by weight, preferably 5 to 50% by weight. 70% by weight
If it exceeds, the impregnated organic porous polymer will not be able to maintain an independent particle state and will be in a state like agglomeration or sludge, and the next polymerization will not proceed stably or is not impregnated in the organic porous polymer. Since the catalyst component is present and a prepolymerization catalyst of ultrafine particles is generated by the prepolymerization, it is not preferable. The residual amount of the inert solvent influences the activity during the gas phase prepolymerization, and the residual amount of about 5% by weight or more makes it easier to control the gas phase prepolymerization.

The above impregnation operation is usually carried out under an inert atmosphere, but the temperature during the operation is carried out within the range of -78 ° C to 100 ° C, preferably -78 ° C to 50 ° C. The time required for the impregnation step is arbitrary, but is generally within 24 hours, preferably within 10 hours. The amounts of the component (i), the component (ii) and the component (iii) used are arbitrary, but generally 0.1 g to 10 g of the alumoxane of the component (ii), preferably 0. 3g to 5
The range is g. If it is less than 0.1 g, the activity per solid catalyst is not sufficiently obtained, and if it exceeds 10 g, alumoxane not impregnated remains as independent particles,
It is not preferable because the particles are combined with the component (iii) to develop the activity and form a fine particle polymer. Ingredient (iii)
The amount used is also arbitrary, but in general, the molar ratio per aluminum atom of component (ii) is 1 to 10,000, preferably 10 to 3000, and more preferably 30 to 1000.
It is a range.

Then, the impregnated solid component consisting of the component (i), the component (ii) and the component (iii) obtained above is brought into contact with an olefin under gas phase conditions to carry out prepolymerization. Monomers used for prepolymerization include ethylene, propylene, butene-1,3-methylbutene-1, and mixtures thereof. In addition, hydrogen may be used together during the prepolymerization, if necessary, to control the molecular weight. The prepolymerization is -78 ° C to 100 ° C, preferably -78 ° C.
C. to 50.degree. C. Pre-polymerization time is 1 minute ~
24 hours, preferably 5 minutes to 10 hours,
The amount of prepolymerization is the same as that of component (ii) and component (ii) in component (i).
0.01 g to 500 g, preferably 0.1 g to 100 g, more preferably 0.2 g to 3 g per 1 g of the impregnated solid component obtained by impregnating i).
The range is 0 grams. If the amount is less than 0.01 g, the effect of gas phase prepolymerization does not appear, and the catalyst components of component (ii) and component (iii) are released from the solid catalyst during the main polymerization, which is not preferable. With a prepolymerization amount of 500 g or more, the reaction product belongs to a polymer rather than a solid catalyst, and not only the activity in the main polymerization is lowered but also handling of the catalyst (feeding method, structure of catalyst tank, etc.) becomes difficult, which is preferable. Absent.

[Use of Solid Catalyst / Polymerization of Olefin] Needless to say, the catalyst of the present invention is applied to solvent polymerization using a solvent, but substantially no solvent is used for liquid phase solventless polymerization, gas phase polymerization. It is also applied to polymerization and melt polymerization. It is also applied to continuous polymerization and batch polymerization. As a solvent in the case of solvent polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or in a mixture. Among these polymerizations, the effect of particle formation by the solid catalyst of the present invention is remarkable especially in gas phase polymerization. Polymerization temperature is -78 ~
The temperature is about 200 ° C., preferably −20 to 100 ° C.
The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² -G. In the polymerization, the molecular weight can be controlled by known means such as selection of temperature and pressure or introduction of hydrogen. Needless to say, during the polymerization, the solid catalyst of the present invention and the polymerization monomer can be polymerized, but it is also possible to coexist with an organoaluminum compound for the purpose of improving polymerization activity and preventing catalyst poisoning. Is. Specific examples of such an organoaluminum compound include R ⁵ _3-n Al
X _n or R ⁶ _3-m Al (OR ⁷ ) _m (wherein R ⁵ and R ⁶ may be the same or different, are a hydrocarbon residue or hydrogen atom having about 1 to 20 carbon atoms, and R ⁷ is the number of carbon atoms). 1-2
There is a hydrocarbon residue of about 0, X is halogen, n and m are 0 ≦ n <3 and 0 <m <3, respectively, or those represented by the following general formula (I) or (II).

[0039]

[Chemical 1]

(Where p is 0 to 50, preferably 2 to
25, and R ⁸ is a hydrocarbon residue, preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 4 carbon atoms,
Indicates. ) Specifically, (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum,
(B) Diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, (c) diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride,
(D) Aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide, (v) methylalumoxane, ethylalumoxane,
Aluminoxanes such as isobutylalumoxane and methylisobutylalumoxane are exemplified. It is also possible to use a mixture of a plurality of these. Of these, trialkylaluminum and alumoxane are preferable.

In addition to the solid catalyst of the present invention and an organoaluminum compound which is an optional component, examples of a third component that can be added include active hydrogen-containing compounds such as H ₂ O, methanol, ethanol and butanol, ethers and esters. Examples thereof include electron-donating compounds such as amines, phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane, and other alkoxy-containing compounds.

An olefin polymerized by the catalyst of the present invention,
That is, the olefin used in the polymerization reaction in the method of the present invention has an α-number of 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
It is an olefin. Specifically, for example, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Hexene, 1-octene, 1-decene, 1-dodecene,
There are 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, particularly preferably ethylene, propylene, 1-butene, 1-hexene. These α-olefins may be mixed for use in polymerization. Further, the catalyst of the present invention can also be copolymerized with the above α-olefins and ethylene. Further, other monomers copolymerizable with the above α-olefin, for example, conjugated and non-conjugated dienes such as butadiene, 1,4-hexadiene, 1,8-nonadiene and 1,9-decadiene, or It is also effective for the copolymerization of cyclic olefins such as cyclopentene, cyclobutene, cyclooctene, norbornene and dicyclopentadiene.

[0043]

【Example】

<Example-1> Production of catalyst component (iii) Dimethylsilylbis (tetrahydroindenyl) zirconium dichloride was added to J. Orgmet. Chem. (342) 21-29.
1988 and J. Orgmet. Chem. (369) 359-370 1989 . Specifically, bis (indenyl) dimethylsilane 5.
4 g of tetrahydrofuran was diluted to 150 ml of tetrahydrofuran, cooled to -50 ° C or lower, and 23.6 ml of n-butyllithium (1.6 M / L) was added dropwise over 30 minutes. After the dropping was completed, the temperature was raised to room temperature over 1 hour, and the reaction was performed at room temperature for 4 hours to synthesize a reaction solution A.

200 ml of tetrahydrofuran was introduced into a 500 ml flask which had been purged with nitrogen, and then -50
After cooling to below ℃, 4.38 grams of zirconium tetrachloride was slowly introduced. Then, after the entire amount of the reaction solution A was introduced, the temperature was slowly raised to room temperature over 3 hours. After reacting for 2 hours at room temperature, the temperature was further raised to 60 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, the residue was dissolved in 100 ml of toluene and redistilled to obtain 3.86 g of crude crystals of dimethylsilylbis (indenyl) zirconium dichloride. Then, the crude crystals were dissolved in 150 ml of dichloromethane, introduced into a 500 ml autoclave, and introduced with 5 g of a platinum-carbon (0.5 wt% platinum supported) catalyst, and then H ₂ = 50 kg / cm ^2.
The hydrogenation reaction was carried out under the conditions of G and 50 ° C. for 5 hours. After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under reduced pressure, the residue was extracted with toluene and recrystallized to obtain 1.26 g of the target dimethylsilylbis (tetrahydroindenyl) zirconium dichloride.

Preparation of component (ii) 1 equipped with a stirrer and a reflux condenser fully replaced with nitrogen
100 ml of dehydrated and deoxygenated toluene was introduced into a 000 ml flask. Then, add trimethylaluminum 0.72 to one of the two dropping funnels.
Gram (10 mmol) and 1.96 g (10 mmol) of triisobutylaluminum were diluted to 50 ml of toluene, and toluene containing saturated water was introduced into the other one, and the mixed aluminum solution and saturated water were added at 30 ° C. The contained toluene was fed with equimolar amounts of Al and H ₂ O over 3 hours. After the feed was completed, the temperature was raised to 50 ° C and
Reacted for hours. After completion of the reaction, the solvent was distilled off under reduced pressure.
9 grams of white solid was obtained. The white solid thus obtained was diluted with toluene and measured by ²⁷ Al-NMR. As a result, a spectrum showing a chemical shift of 174 ppm and a half width of 5844 Hz was shown.

As a component (i) for producing a solid catalyst, a porous polypropylene powder manufactured by Akzo (trade name; "Accurel" 200 to 400 μm)
(Classified product) was used. Pore size of this powder 0.05μ
Pore volume between ~ 2.0μ is 1.89cc / g, 0.00
The total pore volume between 6μ and 10μ was 2.54cc / g. Add component (i) to a 300 ml flask with sufficient nitrogen substitution.
3 g of the above-mentioned porous polypropylene manufactured by Akzo Co. and about 1.8 g (0.0228 mol) of methylisobutylalumoxane synthesized above as the component (ii) were dissolved in 40 ml of toluene and introduced. Then, 42 mg (0.94 mmol) of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized above was introduced as the component (iii). After the introduction, toluene was distilled off for 1 hour under a nitrogen stream while stirring at room temperature to allow the polypropylene particles to independently flow. A part thereof was taken out and dried under reduced pressure at 50 ° C., resulting in a weight loss of 15% by weight, and toluene was recovered in the cooling trap.

The impregnated solid obtained above was prepolymerized with propylene under atmospheric pressure in a flow system. The pre-polymerization was carried out by cooling with ice water while controlling the propylene gas flow rate to 10
Performed for 30 minutes between ~ 20 ° C. The polymerization temperature was controlled by cooling with ice water and changing the mixing ratio of propylene and nitrogen in the circulating gas. After the completion of the prepolymerization, the solid was collected, and as a result, 11.5 g of solid was obtained. The Zr content in this solid was 0.71 mg / gram. Therefore, the prepolymerization yield was 800 grams per Zr.

Polymerization of propylene Into a stirring autoclave having an internal volume of 1.5 liters, 80 g of sodium chloride which had been thoroughly dehydrated and replaced with nitrogen was introduced,
The temperature inside the autoclave was raised to 50 ° C. and propylene was replaced. Then, 0.6 g of the solid catalyst obtained above was introduced, propylene pressure = 7 Kg / cm ² G, polymerization temperature = 50.
Gas phase polymerization was carried out under the conditions of ° C and polymerization time = 2 hours. After the completion of the polymerization, the solid was recovered, washed with a large amount of water to wash the salt, and then dried to recover 22 g of the polymer. Therefore, it was 51.6 kg per gram of Zr. The melting point is 127.7 ° C., the result of ¹³ C-NMR measurement is
[Mm] triad fraction was 0.86, number average molecular weight measured by GPC was 14,700, and Q value (Mw / Mn) was 2.4.
6. The average particle size was 1.6 mm.

<Example-2> Polymerization time of propylene was 6
Polymerization was performed under the same conditions as in Example 1 except that the time was set. Table 1 shows the results.

<Example-3> The solid catalyst obtained in Example-1 was stored for one month in a nitrogen atmosphere and then polymerized under the same conditions as in Example-1. Table 1 shows the results.

<Examples 4 to 6> In the polymerization of propylene in Example 1, as an optional component (B) in addition to the solid catalyst (0.6 g), polymethylalumoxane manufactured by Tosoh Akzo (association degree = 16-mer), the same polyisobutylalumoxane, and triisobutylaluminum were each used in the same manner as in Example 1 except that 0.11 g of each was also used. Table 1 shows the results.

<Example-7> Production of solid catalyst Instead of methylisobutylalumoxane as the component (ii),
Tosoh Akzo's methyl isobutyl alumoxane, trade name "MMAO" (modified methyl alumoxane) 2.5
g, a solid catalyst was prepared under the same conditions as in Example 1 except that 70.7 mg of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride of component (iii) was used. It is to be noted that the east Akzo Co., Ltd. to "MMAO", ²⁷ Al
-A broad spectrum showing a full width at half maximum of 6550 Hz at 190 ppm was obtained as measured by NMR. The toluene content in the impregnated solid was about 8 weight percent. The Zr content in the obtained catalyst solids after prepolymerization was 1.21 mg / gram, and the prepolymerization yield per gram of Zr was 440. Polymerization of Propylene 0.5 g of the solid catalyst obtained above, the same as the one used in the production of the above solid catalyst, “MMA manufactured by Tosoh Akzo Co., Ltd.”
Polymerization was performed under the same conditions as in Example 1 except that 0.12 g of "O" was used. Table 2 shows the results.

Comparative Example-1 Production of Solid Catalyst Component (i), Component (ii) and Component (ii) as in Example-1
3 g, 1.8 g, and 46 mg of i) were used, and these were dissolved in 40 ml of a toluene solvent and mixed. Then, 60 ml of n-heptane was added to precipitate the reaction product, and then, in the slurry state, propylene gas was fed in a flow system under atmospheric pressure to carry out prepolymerization at 20 ° C./30 minutes. After the completion of prepolymerization, the supernatant was removed by decantation, and n-
After washing with 200 ml of heptane three times, the solvent was distilled off under reduced pressure to obtain 10.5 g of a target solid catalyst. In this solid catalyst, zirconium is 0.6
It contained 1 milligram / gram, and the prepolymerization yield was about 890 (gram / gram Zr). Polymerization of Propylene Polymerization was carried out under the same conditions as in Example 1 except that 0.8 g of the solid catalyst obtained above was used. Table 1 shows the results. This powder contains a large amount of fine powder of 300 μm or less, which is not preferable in the vapor phase polymerization operation.

<Examples 8 and 9> Porous polypropylene powder manufactured by Akzo Co., Ltd. as a component (i) for producing a solid catalyst (trade name: "Accurel"<100 μ classified product)
4 g was used. The pore size of this powder is 0.0
Pore volume between 5μ and 2.0μ is 1.66cc / g,
The total pore volume between 006 and 10μ was 2.33 cc / g. As the component (ii), 2.5 g of the same "MMAO" manufactured by Tosoh Akzo Co., Ltd. as used in Example-7 and 56.3 dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized in Example-1 were used. After diluting milligram to 40 milliliter of toluene and introducing it to the component (i), toluene was distilled off by nitrogen stream for 30 minutes to produce an impregnated solid. The toluene content was about 6 weight percent. Then, prepolymerization was carried out at 10 to 20 ° C. for 30 minutes in a propylene stream in the same manner as in Example 1 to obtain 12.8 g of a target solid catalyst. The content of Zr was 0.82 mg / g and the prepolymerization yield was 600 g / gZr. Polymerization of Propylene Using 0.6 g of the solid catalyst obtained above, the polymerization operation was carried out under the same conditions as in Example-1 or Example-7, except that the above procedure was used. Table 2 shows the results.

<Examples 10 and 11> Preparation of component (i) In a 2000 ml glass flask, polypropylene powder (measured by porosimeter, the product having a pore size of 0.
The pore volume (cc / g) in the range of 006 to 10 μm is 0.
016 cc / g, average pore size 160 angstrom, powder particle average particle size 210-300 μm) was introduced into 20 g, and then n-heptane 320 ml, n-octane 12
80 ml and 1 g of fluorite were introduced, and the mixture was stirred and the temperature was raised to the boiling point of the mixed solvent. The mixed solvent was extracted 15 minutes after the boiling point was reached, and the polypropylene powder was dried with nitrogen. By this extraction work, a porous polypropylene powder that meets the purpose of the present invention (as a result of porosimeter measurement, this powder has a pore size of 0.05 to
Pore volume between 2 μm 0.981 cc / g, 0.00
The pore volume of 6 to 10 μm was 1.14 cc / g, and the average particle diameter of powder particles was 210 to 300 μm).

Production of Solid Catalyst 4 g of the component (i) obtained above, 2.5 g of the same "MMAO" manufactured by Tosoh Akzo Co., Ltd. as used in Example-7, component (ii)
A solid catalyst was prepared under the same conditions as in Example-7 except that 48.5 mg of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was used as i).
9.8 grams of solid catalyst was obtained. Zr is 0.
93 mg / g, prepolymerization yield was about 350 g / g Zr. Polymerization of Propylene Polymerization was carried out under the same conditions as in Examples 1 and 7, except that 0.6 g of the solid catalyst obtained above was used.
Table 2 shows the results.

<Comparative Examples-2 and 3> A solid catalyst was produced by using polypropylene powder as a component (i) before extraction treatment with a mixed solvent of n-heptane and n-octane in Examples-10 and 11. Zr content is 0.70 mg / gram, prepolymerization yield is 880 (gram / gram Z
r). Polymerization of propylene was carried out in Examples-1 and 7
The same conditions were used. Table 2 shows the results.

<Comparative Examples 4,5> Polymerization was carried out under the same conditions as in Comparative Examples 1 and 2, except that 4 g of silica ( ^# 952) manufactured by Fuji Davidson Co., Ltd. was used as the component (i).
Table 2 shows the results. The Zr content is 0.9
The 7 milligram / gram prepolymerization yield was about 330 (gram / gram Zr).

<Comparative Example-6> The solid catalyst prepared in Comparative Example-4 was stored for one month in a nitrogen atmosphere and then polymerized under the same conditions as in Comparative Example-1. Table 2 shows the results.

<Example-12> Preparation of Component (iii) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was synthesized by the following method. Add THF2 to a 500 ml flask with sufficient nitrogen substitution.
After introducing 00 ml and 5 g of fluorene and cooling to -50 ° C or lower, a diluted solution of methyllithium diethyl ether (1.
After 67 ml of 4 M) was added dropwise over 30 minutes, the temperature was gradually raised to room temperature and the reaction was carried out for 3 hours. Then, after cooling again to -50 ° C or lower, 10 g of 6,6-dimethylfulvene was added to 30 g.
It dripped over minutes. After completion of the dropping, the temperature was slowly raised to room temperature and the reaction was performed for 2 days and nights. After completion of the reaction, the reaction was stopped by adding 60 ml of H ₂ O, the ether layer was separated, and anhydrous MgSO 4 was added.
After dehydration using ₄ , the ether was evaporated to dryness to obtain 17.6 g of 2-cyclopentadienyl 2-fluorenylpropane crude crystal. Then, 10 g of the above crude crystals were diluted with 100 ml of THF, cooled to -50 ° C or lower, and 46.0 ml (0.0736) of n-butyllithium.
Mol) was added dropwise over 10 minutes. The mixture was returned to room temperature over 1 hour and reacted at room temperature for 2 hours. Next, under a nitrogen stream,
After evaporation of the solvent to dryness, dichloromethane 100
ml was added, and the mixture was cooled to -50 ° C or lower. Then, in advance to a low temperature of 50 ml of dichloromethane, zirconium tetrachloride 8.1.
The mixed solution of 6 g was fed all at once. After mixing 3
The temperature was slowly raised over time, and the reaction was carried out at room temperature for one day. After the reaction was completed, the solid matter was removed by filtration, and the filtrate was concentrated and recrystallized to give 4.68 g of red isopropylidene (cyclopentadienyl) (fluorenyl).
A zirconium dichloride component (iii) was obtained.

Production of Solid Catalyst A solid catalyst was produced in the same manner as in Example-7 except that 65.5 mg of the component (iii) obtained above was used.
The Zr content was 0.88 (milligram / gram), and the prepolymerization yield was 650 (gram / gram Zr). Polymerization of Propylene Polymerization was carried out under the same conditions as in Example-7 except that 0.8 g of the solid catalyst obtained above was used. Table 3 shows the results.

Example 13 Preparation of Component (iii) Dimethylsilylenebis (2-methylindenyl) zirconium dichloride was prepared by the following method. In a 500 ml glass reaction vessel, 4.3 g of 2-methylindene (3
(3 mmol) was dissolved in 80 ml of tetrahydrofuran, and under cooling, 21 ml of a 1.6M hexane solution of n-butyllithium was dissolved.
Was slowly dropped into the reaction vessel. After stirring at room temperature for 1 hour, the mixture was cooled again, 2.1 g of dimethyldichlorosilane was slowly added dropwise, and after stirring at room temperature for 12 hours, 50 ml of water was added, the organic phase was separated and dried, and dimethylbis (2- 3.5 g of methylindenyl) silane was obtained. 3.5 g of dimethylbis (2-methylindenyl) silane obtained by the above method
Was dissolved in 7.0 ml of tetrahydrofuran and, under cooling, n-
13.9 ml of 1.6M hexane solution of butyllithium was slowly added dropwise. After stirring at room temperature for 3 hours, 2.6 g (11 mmol) of zirconium tetrachloride / 60 tetrahydrofuran
The solution was slowly added dropwise to the ml solution, stirred for 5 hours, blown with hydrogen chloride gas, and then dried. Subsequently, methylene chloride was added to separate the soluble matter, and the soluble matter was crystallized at a low temperature to give a 0.1.
45 g of orange powder was obtained.

Production of Solid Catalyst A solid catalyst was produced in the same manner as in Example-7 except that 98 mg of the component (iii) obtained above was used.
The Zr content was 1.35 mg / gram, and the preliminary polymerization yield was 430 (gram / gram Zr). Polymerization of Propylene Polymerization was carried out under the same conditions as in Example-7 except that 1.0 g of the solid catalyst obtained above was used. Table 3 shows the results.

Example 14 Synthesis of Component (iii) Ethylenebis (indenyl) zirconium dichloride
It was synthesized according to J. Orgmet. Chem. (288) 63-67 1985 . Production of Solid Catalyst A solid catalyst was produced in the same manner as in Example-7 except that 60.8 mg of the component (iii) obtained above was used. The Zr content was 1.02 mg / gram, and the preliminary polymerization yield was 350 (gram / gram Zr). Polymerization of Propylene Polymerization was carried out under the same conditions as in Example-7 except that 1.0 g of the solid catalyst obtained above was used. The results are shown in Table 3.
It was shown to.

Example 15 Production of Propylene / Ethylene Random Copolymer 80 g of fully dehydrated and nitrogen-substituted sodium chloride was introduced into a stirring autoclave having an internal volume of 1.5 l.
The inside of the autoclave was heated to 30 ° C. and propylene was replaced. Then, 0.8 g of the solid catalyst obtained in the production of the solid catalyst of Example-1 was introduced, and the propylene pressure was 7 kg / cm.
² G and ethylene were fed at a rate of 0.0375 g / min to carry out gas phase polymerization under the conditions of polymerization temperature = 30 ° C. and polymerization time = 2 hours. After completion of the polymerization, the solid was recovered, washed with a large amount of water to wash the salt, and then dried.
3 grams of polymer were recovered. Therefore, it was 51.6 kg per gram of Zr. Melting point is 117.2 ° C, ¹³
As a result of C-NMR measurement, the [mm] triad fraction was 0.
93, the ethylene content was 3.01 mol%, the number average molecular weight measured by GPC was 23,700, the Q value (Mw / Mn) was 2.28, and the average particle size was 1.6 mm.

<Example 16> Polymerization of ethylene 80 g of salt which had been dehydrated and replaced with nitrogen was introduced into a stirring autoclave having an internal volume of 1.5 liters, and the mixture was heated to 80
The temperature was raised to ° C and ethylene substitution was performed. Next, using 0.5 g of the solid catalyst produced in Example-4, 50 cc of hydrogen was fed, and then a polymerization operation was carried out at 85 ° C. for 2 hours at an ethylene pressure of 7 kg / Cm ² G. The catalytic activity is 96. per gram of Zr.
It was 3 kg. As a result of GPC measurement, Mn = 21,50
It was 0 and Q = 2.88.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

INDUSTRIAL APPLICABILITY According to the present invention, a polymer having a small amount of ash components such as an inorganic oxide, particularly a propylene-based polymer which has been difficult to obtain in the past, can be obtained in a good particle shape with a high yield. That is why it is possible to improve the activity persistence and the storage stability as described above in the section "Summary of the Invention".

[Brief description of drawings]

FIG. 1 is intended to help understanding of the technical content of the present invention regarding a Ziegler catalyst.

Claims (3)

[Claims] 1. A prepolymerization comprising impregnating component (ii) and component (iii) in the following component (i), and then contacting this with an olefin under gas phase conditions for polymerization. A solid catalyst for α-olefin polymerization, which is obtained by the above. Component (i): an organic porous polymer having an average particle size of 5 to 1000 μm and a pore size of 0.006 to 10 μm
The total pore volume of all pores is 0.3 cc / g or more, and the total pore volume of all pores having a pore diameter of 0.05 to 2 μm is 0.006 to 50% or more of the total pore volume of all pores having a size of 10 μm, component (ii); alumoxane, component (iii); periodic table IVB to VIB having at least one conjugated five-membered ring ligand Group transition metal compounds. 2. A method for producing an α-olefin polymer, which comprises contacting an α-olefin with the solid catalyst for polymerization of α-olefin according to claim 1 to polymerize it. 3. An α-olefin is brought into contact with the catalyst comprising the solid catalyst for α-olefin polymerization of claim 1 and an organoaluminum compound to polymerize the α-olefin.
-Process for producing olefin polymers.