JP3202358B2 - Catalyst for .ALPHA.-olefin polymerization and method for producing .ALPHA.-olefin polymer using the catalyst - Google Patents

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 method 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 using 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 using a combination of a zirconocene compound and alumoxane has been proposed (Japanese Patent Laid-Open Nos. 58-19309 and 60-35007). In addition, 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). These proposals can produce a polymer having high activity and a narrow molecular weight distribution, but on the other hand, the catalyst is soluble in toluene as a solvent and thus has a very small particle size (usually about 1 to 50 μm). 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 brought into contact with each other in advance to granulate the produced polymer. However, particles can be formed by this method only in so-called liquid phase bulk polymerization using a propylene solvent, and a slurry polymerization or a gas phase polymerization using an inert solvent cannot obtain a polymer having a controlled particle size.

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 techniques have enabled the production of granular polymers even in the case of gas phase polymerization, but the activity per supported catalyst is low because the catalyst components supported on silica are limited, 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, loading of a catalyst component on polyethylene particles is proposed. 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 a carrier, but it is difficult to support the catalyst component as compared with the inorganic oxide, the activity is low and the support 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 with the prior art. It is intended to provide a method for producing a coalescence.

[0006]

[Wherein (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 each a conjugated five-membered ring ligand] Represents. Q represents a bonding group that bridges the two conjugated five-membered ring ligands, and S represents a bonding group that bridges the conjugated five-membered ring ligand and the Z group. Z is oxygen, sulfur, an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or carbon. It is a phosphorus-containing hydrocarbon group of the number 1-40. R ¹ , R ² and R ³ are each a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon. It is a base. a is 0 or 1. b, c and d are 0≦b≦5, 0≦c≦5 and 0≦d≦5 when a is 0, and 0≦b≦4 and 0≦c≦ when a is 1. 4, an integer that satisfies 0≦d≦4. X and Y are each hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or 1 to 1 carbon atoms. 20 silicon-containing hydrocarbon groups. Me is titanium, zirconium or hafnium. ]

Further, the method for producing an α-olefin polymer according to the present invention is the solid catalyst for α-olefin polymerization as described above,
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 above solid catalyst for α-olefin polymerization and an organoaluminum compound to polymerize the polymer. To do.

<Effect> 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 with a good particle property in a high yield. It is also possible to improve the activity durability and storage stability of the catalyst. It is understood that such an effect is completely unpredictable from the prior art.

[Detailed Description of the Invention] [Solid Catalyst for α-Olefin Polymerization] The catalyst for α-olefin polymerization according to the present invention is prepared by impregnating component (i) with component (ii) and component (iii). It was obtained. Here, "the product obtained by impregnating component (i) with component (ii) and component (iii)" means impregnating only component (ii) and component (iii) into component (i). In addition to those obtained by the above, those obtained by impregnating other components other than the component (ii) and the component (iii) are included.

<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 the pores of 0.006 to 10 μm is 0.8 cc/g or more, preferably 1.0 cc/g or more, and the pore diameter is 0.05 to 2
The total pore volume of all pores having a diameter of μm is 0.0
50% of the total pore volume of all pores having a size of 06 to 10 μm
The above is preferably 60% or more. In this component (i), when the total pore volume of all pores having a pore diameter of 0.006 to 10 μm is less than 0.8 cc/g, the amount of the catalyst component that can be impregnated in the component (i) is Is low, it is impossible to obtain sufficient activity per catalyst. Impregnation of the catalyst component, especially alumoxane, is difficult for the 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 the polymerization to start or continue the polymerization. Therefore, it is not preferable because it causes formation of fine particle polymer. Here, the pore volume and the pore diameter are measured by 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. Is used to obtain a number average particle size distribution, which is converted into a weight average particle size distribution, and means a value when the weight is 50%, that is, D ₅₀ .

The kind of polymer of the organic porous polymer having the above characteristics is arbitrary as long as the above conditions are satisfied, but in general, (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. Of 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 together, and it is also possible to use alumoxanes in combination with other alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride.

It is also possible to use 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 are methylalumoxane and methylisobutylalumoxane. Of these, ²⁷ A
Chemical shift in l-NMR measurement is 160 to 250
Methylisobutylalumoxane, which is characterized in that it has a line width of 3000 Hz or more and is located between 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 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 a suitable 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 or aluminum sulfate hydrate, ( F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum, (to) methylalumoxane and isobutylalumoxane are synthesized by a known method, and these two components are mixed in predetermined amounts. A method of mixing and reacting by heating.

<Component (iii)> The component (iii) is a transition metal compound of Group IVB to VIB of the Periodic Table having at least one conjugated five-membered ring ligand and has the following general formula (1) or ( It is a transition metal compound represented by 2). Q _a (C ₅ H _5-ab R ¹ _b )(C ₅ H _5-ac R ² _c )MeXY (1) S _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
The conjugated five-membered ring ligands represented by (H _5-ac R ² _c ) and (C ₅ H _5-ad R ³ _d ) 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 (without a 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 five-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 group, a halogen group (eg fluorine, chlorine, 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) (R') is a group having about 1 to 18 carbon atoms). 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 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, an amino group, 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 bridging 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, (5) 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) Ethylenebis(indenyl)zirconium monohydride monochloride, (4) ethylenebis(indenyl)methylzirconium 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-dimethylcyclopentadienyl)zirconium chloride 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, for example, (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, ( 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-t-butylfluorenyl)zirconium dichloride, (28) dimethylsilylene (2,5-dimethylcyclopentadienyl) (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 5-membered ring ligand bridged with a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, for example,

(1) Dimethylgermanium bis(indenyl) zirconium dichloride, (2) Dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) Methylaluminum bis(indenyl) zirconium dichloride, (4) Phenylaluminum bis (Indenyl)zirconium dichloride, (5) phenylphosphinobis(indenyl)zirconium dichloride, (6) ethylholanobis(indenyl)zirconium dichloride, (7) phenylaminobis(indenyl)zirconium dichloride, (8)
Examples include phenylamino(cyclopentadienyl)(fluorenyl)zirconium dichloride and the like.

(E) Transition metal compounds having one 5-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)
Examples include dimethylgermane (tetramethylcyclopentadienyl)(phenyl)aminozirconium dichloride and the like. (F) Further, it is also possible to use a compound in which chlorine in the compounds (a) to (e) is replaced with bromine, iodine, hydride, methyl, phenyl or the like.

Further, in the present invention, as the component (iii), compounds in which the central metal of the zirconium compounds exemplified in the above (a) to (f) are changed from zirconium to titanium or hafnium can also be used. Of these, preferred are zirconium compounds and hafnium compounds crosslinked with an alkylene group or a silylene group. Particularly preferred is a zirconium compound having a substituent at the 2-position adjacent to the carbon having a bridging group.

<Preparation of Solid Catalyst> The solid catalyst of the present invention comprises
It is obtained by impregnating component (i) with component (ii) and component (iii). 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 it can be dissolved. A method of dissolving and mixing with the component (i), and then distilling off the solvent under reduced pressure or in an inert gas stream, (b) the component (ii) and the component (iii) are dissolved in an inert solvent, and then a 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 liquid obtained above can be retained in the particles, and (c) the solution of the component (ii) and the component (iii) are sequentially added. To impregnate component (i) physically,
Etc. are illustrated.

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 varies depending on the pore volume of the organic porous polymer (component (i)) used, but is 5 to 50% by weight with respect to the organic porous polymer after impregnation. If it exceeds 50% by weight, the impregnated organic porous polymer cannot maintain the independent particle state and becomes a state like aggregation or sludge, and the next polymerization does not proceed stably, or it is impregnated in the organic porous polymer. It is not preferable because there is a catalyst component which is not treated and a fine particle polymer is generated during the polymerization. The residual amount of the inert solvent influences the activity during the polymerization, particularly during the gas phase polymerization, and the residual amount of about 5% by weight or more facilitates the stable activation, so that the polymerization control is easy. The above-mentioned impregnation operation is usually carried out in an inert atmosphere, but it may be impregnated while prepolymerizing in the presence of a monomer, or may be impregnated after a small amount of prepolymerization. As such a monomer, ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene-1,1,5-hexadiene, styrene, divinylbenzene or the like, or a mixture thereof is used. The temperature during the impregnation operation is -78°C
It is carried out in the range of 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.

Component (i), component (ii) and component (iii)
The amount of the alumoxane of the component (ii) is generally 0.1 to 10 g per 1 g of the component (i),
The range is preferably 0.3 g to 5 g. 0.1 g
In the following, the activity per solid catalyst is not sufficiently obtained, and if it exceeds 10 g, alumoxane that is not impregnated remains as independent particles, and the particles are combined with the component (iii) to exhibit the activity, and thus the fine particle polymer. Is not preferable because it produces The amount of the component (iii) used is also optional, but generally it is 1 in terms of the molar ratio per aluminum atom of the component (ii).
The range is from about 10,000, preferably from 10 to 3000, more preferably from 30 to 1000.

[Use of Solid Catalyst/Olefin Polymerization] The catalyst of the present invention is also applied to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially without using a solvent. It is also applied to continuous polymerization and batch polymerization. Among these polymerizations, the effect of particle formation by the solid catalyst of the present invention is particularly remarkable in gas phase polymerization.

The polymerization temperature is about -78 to 200°C, preferably -20 to 100°C. The olefin pressure of the reaction system is not particularly limited, but is preferably atmospheric pressure to 50 kg/cm ^2.
-G range. In the polymerization, known means,
For example, the molecular weight can be controlled by selecting the temperature and pressure or introducing hydrogen. It is needless to say that the solid catalyst of the present invention and the polymerization monomer can be polymerized in the polymerization, but it is also possible to coexist with an organoaluminum compound for the purpose of improving the polymerization activity and preventing catalyst poisoning. Is. Specific examples of such an organoaluminum compound include R ⁵ _3-n AlX _n or R ⁶ _3-m A
l(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 a hydrocarbon residue having about 1 to 20 carbon atoms. A group, X is halogen, n and m are 0≦n<3,
0<m<3) or one 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) trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum,
(B) Alkyl aluminum halides such as diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) alkyl aluminum hydrides such as diethyl aluminum hydride and 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.
The 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 is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Specifically, for example, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, 1-hexene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., particularly preferably ethylene, propylene, 1
-There are butenes and 1-hexenes. These α-olefins can be mixed for use in polymerization.
Further, the catalyst of the present invention is also capable of copolymerizing the above α-olefins with ethylene. Furthermore, other monomers copolymerizable with the α-olefin, such as butadiene,
1,4-hexadiene, 1,8-nonadiene, 1,9-
It is also effective for the copolymerization of conjugated and non-conjugated dienes such as decadiene, or cyclic olefins such as cyclopentene, cyclobutene, cyclooctene, norbornene and dicyclopentadiene.

[0042]

【Example】

<Example-1> Production of component (iii) Dimethylsilylenebis(2-methylindenyl)zirconium dichloride was produced by the following method. In a 500 ml glass reaction vessel, 4.3 g of 2-methylindene (3 g
3 mmol) was dissolved in 80 ml of tetrahydrofuran, and under cooling, 21 ml of 1.6 M 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. Dimethylbis(2-methylindenyl)silane obtained by the above method 3.5
g was dissolved in 7.0 ml of tetrahydrofuran and, under cooling, n
13.9 ml of 1.6 M hexane solution of -butyllithium was slowly added dropwise. After stirring at room temperature for 3 hours, 2.6 g (11 mmol) of zirconium tetrachloride/tetrahydrofuran 6
The solution was slowly added dropwise to a 0 ml solution, stirred for 5 hours, blown with hydrogen chloride gas, and then dried. Subsequently, methylene chloride was added to separate the soluble portion and crystallize at low temperature,
0.45 g of orange powder was obtained.

Preparation of component (ii) 1 equipped with a stirrer and a reflux condenser fully replaced with nitrogen.
In a 000 ml flask, dehydrated and deoxygenated toluene 10
0 ml was introduced. Then, on one of the two dropping funnels,
0.72 g (10 mmol) of trimethylaluminum,
1.96 g (10 mmol) of triisobutylaluminum was diluted with 50 ml of toluene, and toluene containing saturated water was introduced into the other one, and the mixed aluminum solution and the toluene containing saturated water were mixed with Al and H ₂ O at 30° C. Was fed in equimolar amounts over 3 hours. After the end of feed, 5
The temperature was raised to 0° C. and the reaction was performed for 2 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain 1.9 g of a white solid. The obtained white solid was diluted with toluene and measured by ²⁷ Al-NMR. As a result, a spectrum having a chemical shift of 174 ppm and a half width of 5844 Hz was shown.

Porous polypropylene powder (trade name: “Accurel” 200 to 400 μm classified product) manufactured by Akzo was used as the component (i) for producing the solid catalyst . Pore size of this powder is 0.05μm~
The pore volume between 2.0 μm is 1.89 cc/g, 0.00
The total pore volume between 6 μm and 10 μm was 2.54 cc/g. To a 300 ml flask sufficiently replaced with nitrogen, 3 g of the above-mentioned Akzo porous polypropylene as component (i) and 2.0 g (0.025 mol) of methylisobutylalumoxane synthesized above as component (ii) were added to toluene. It was dissolved in 40 ml and introduced. Then component (iii)
As the above, 95.2 mg of dimethylsilylenebis(2-methylindenyl)zirconium dichloride synthesized above was introduced, and toluene was distilled off for 1 hour under a nitrogen stream while stirring at room temperature to obtain a target solid catalyst. .. A small amount of this solid catalyst was sampled and dried under reduced pressure at 50°C.
The weight was reduced by weight, and toluene was recovered in the cold trap.

Polymerization of Propylene 80 g of fully dehydrated and nitrogen-substituted sodium chloride was introduced into a stirring autoclave having an internal volume of 1.5 liter, and then the temperature in the autoclave was raised to 50° C. to replace propylene. Next, 0.5 g of the solid catalyst obtained above was introduced, and propylene pressure=7 kg/cm ² G, polymerization temperature=50° C., polymerization time=2.
Gas phase polymerization was carried out under the conditions of time and time. 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 17.5 g of a polymer. Therefore Z
It was 10.3 kg per 1 g of r. Melting point 140.7
As a result of ¹³ C-NMR measurement at 0°C, the [mm] triad fraction was 0.88, and the number average molecular weight measured by GPC was 11
The value was 2,000, the Q value (Mw/Mn) was 2.35, and the average particle size was 1.6 mm. The amount of fine particles of 149 μm or less was 0.5% by weight.

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

<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. The results are shown in Table 1.

<Examples 4 to 6> In the polymerization of propylene in Example 1, 0.6 g of the solid catalyst and optional component (B) were used.
Polymerization was carried out under the same conditions as in Example 1 except that a predetermined amount of polymethylalumoxane (association degree=16-mer), polyisobutylalumoxane and triisobutylaluminum manufactured by Tosoh Akzo Co., Ltd. was used together. The results are shown in Table 1.

<Example-7> As a component (i) for producing a solid catalyst , 4 g of porous polypropylene powder (trade name: "Accurel"<100 μm classified product) manufactured by Akzo was used. The pore size of this powder is 0.05 μm ~
Pore volume between 2.0 μm is 1.66 cc/g, 0.00
The total pore volume between 6 and 10 μm was 2.33 cc/g. Methylisobutylalumoxane manufactured by Tosoh Akzo Co., Ltd. as the component (ii), trade name: “MMAD” (Modified Meth
ylaluminoxane), 86.6 mg of dimethylsilylenebis(2-methylindenyl)zirconium dichloride synthesized in Example-1 was diluted with 60 ml of toluene,
It was dripped on the component (i) over 30 minutes. After the dropping was completed, toluene was distilled off at room temperature by a nitrogen stream to obtain the desired solid catalyst. The product name "MMAO" manufactured by Tosoh Akzo Co., Ltd. was measured by ²⁷ Al-NMR.
A broad spectrum was obtained showing a full width at half maximum of 6550 Hz at 0 ppm. The toluene content in the solid catalyst was 9% by weight. Polymerization of Propylene Under the same conditions as in Example 1, except that 0.5 g of the solid catalyst obtained above and 0.12 g of the trade name "MMAO" manufactured by Tosoh Akzo Co., Ltd. used in the production of the above solid catalyst were used. A polymerization operation was performed. The results are shown in Table 2.

<Example-8> 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 in Example-7 was used. The results are shown in Table 2.

<Examples 9 and 10> Preparation of component (i) In a 2000 ml glass flask, polypropylene powder (as a result of porosimetry measurement, this product had 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) were introduced into 20 g, 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 the porosimeter measurement, this powder has a pore size of 0.05
Pore volume between 0.92 cc/g and 0.0
A pore volume of 06 to 10 μm was 1.14 cc/g, and an average particle diameter of powder particles was 210 to 300 μm).

Production of solid catalyst 4 g of the component (i) obtained above, MMA manufactured by Toso Akzo Co., Ltd.
2.5 g of O and 7 g of dimethylsilylenebis(2-methylindenyl)zirconium dichloride as component (ii)
A solid catalyst was produced under the same conditions as in Example-7 except that 1.5 mg was used. Polymerization of Propylene Example except using the solid catalyst obtained above-
Polymerization was carried out under the same conditions as 7 and 8. The results are shown in Table 2. Comparative Examples-1 and 2 All of Examples-9 and 10 except that polypropylene powder before extraction treatment with a mixed solvent of n-heptane and n-octane in Examples-9 and 10 is used as the component (i). Polymerization operation was carried out under the same conditions. The results are shown in Table 2.

<Comparative Examples 3 and 4> 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 Devison Co., Ltd. was used as the component (i). The results are shown in Table 2.

<Comparative Example-5> The solid catalyst prepared in Comparative Example-3 was stored in a nitrogen atmosphere for one month and then polymerized under the same conditions as in Comparative Example-4. The results are shown in Table 2.

Example 11 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 4M) was added dropwise over 30 minutes, the temperature was gradually raised to room temperature and the reaction was carried out for 3 hours. Then again -50
After cooling below ℃, 6,6-dimethylfulvene 10g
Was added dropwise over 30 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 the reaction was completed, H ₂ O was added to 60
The reaction was stopped by adding ml, and the ether layer was separated.
After dehydration with SO ₄ , the ether was evaporated to dryness to give 2-cyclopentadienyl-2-
17.6 g of crude fluorenylpropane crystals were obtained. Then, 10 g of the above-mentioned crude crystals was diluted with 100 ml of THF and -50
It was cooled to below 0° C. and 46.0 ml (0.
(0736 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, the solvent was evaporated and dried under a nitrogen stream, 100 ml of dichloromethane was added, and the mixture was cooled to -50°C or lower. Next, a solution prepared by previously mixing 8.16 g of zirconium tetrachloride in 50 ml of dichloromethane at low temperature was fed all at once. After mixing, the temperature was slowly raised over 3 hours, and the reaction was allowed to proceed overnight at room temperature. After completion of the reaction, solid matter was removed by filtration, and the filtrate was concentrated and recrystallized to obtain 4.68 g of red isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride component (iii). Production of Solid Catalyst A solid catalyst was produced under the same conditions as in Example-7 except that 62.2 mg of the component (iii) obtained above was used. Polymerization of Propylene Polymerization was carried out under the same conditions as in Example-8 except that 0.6 g of the solid catalyst obtained above was used. Catalytic activity is 3
8,500 g/gZr, melting point 131.5°C, [rr]
Triad fraction 0.84, number average molecular weight 29,10
0, Q value is 2.52, average particle size is 210μm, 105μ
The amount of m or less was 4.5% by weight.

<Example-12> Production of catalyst component (iii) Dimethylsilylbis(tetrahydroindenyl)zirconium dichloride was added to J. Orgmet. Chem. (342) 21-29 19
88 and J. Orgmet. Chem. (369) 359-370 1989 . Specifically, in a 300 ml flask with nitrogen substitution,
After 5.4 g of bis(indenyl)dimethylsilane was diluted with 150 ml of tetrahydrofuran and cooled to -50°C or lower, 23.6 ml of n-butyllithium (1.6M/L) was diluted.
Was added dropwise over 30 minutes. After completion of the dropping, 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. After introducing 200 ml of tetrahydrofuran into a 500 ml flask purged with nitrogen and cooling to -50°C or lower, 4.38 g 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 at room temperature for 2 hours, another 6
The temperature was raised to 0° C. and the reaction was performed for 2 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, the residue was dissolved in 100 ml of toluene, and the solvent was distilled off again 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% by weight platinum-supported) catalyst, and then H ₂ =50 kg/cm ² G at 50° C. The hydrogenation reaction was carried out for 5 hours. After the reaction was completed, 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 desired dimethylsilylbis(tetrahydroindenyl)zirconium dichloride. Synthesis of Solid Catalyst A solid catalyst was produced under the same conditions as in Example-7 except that 68.5 mg of the component (iii) obtained above was used. Polymerization of Propylene Polymerization was carried out under the same conditions as in Example-8 except that 0.6 g of the solid catalyst obtained above was used. Catalytic activity is 5
8,800 g/gZr, melting point 125.3° C., [mm] triad 0.85, number average molecular weight 14500, Q value 2.33, average particle size 255 μm, particle size less than 105 μm 20. It was 6% by weight.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

INDUSTRIAL APPLICABILITY 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, is obtained in a good particle shape and a high yield. That is, the activity persistence and the storage stability can be improved as described above in the section of "Summary of the Invention".

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-25348 (JP, A) JP-A-63-152608 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (3)

(57) [Claims] 1. A product obtained by impregnating the following component (i) with component (ii) and component (iii), wherein the residual amount of the inert solvent in the impregnated state is the organic porosity after impregnation. Solid catalyst for α-olefin polymerization, characterized by being applied to liquid phase solventless polymerization, gas phase polymerization and melt polymerization, which is 5 to 50% by weight based on the quality polymer, and which is substantially free of solvent. .. 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 sum of the pore volumes of all the pores is 0.8 cc/g or more, and the total sum of the pore volumes of all the pores having the 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); a transition metal compound having at least one conjugated five-membered ring ligand, A transition metal compound represented by the following general formula (1) or (2). Q _a (C ₅ H _5-ab R ¹ _b )(C ₅ H _5-ac R ² _c )MeXY (1) S _a (C ₅ H _5-ad R ³ _d )ZMeXY (2) [where (( ^{_{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) , respectively, represent a conjugated five-membered ring ligands. Q represents a bonding group that bridges the two conjugated five-membered ring ligands, and S represents a bonding group that bridges the conjugated five-membered ring ligand and the Z group. Z is oxygen, sulfur, carbon number 1
To C20 alkoxy group, C1 to C20 thioalkoxy group, C1 to C40 silicon-containing hydrocarbon group, C1 to C40 nitrogen containing hydrocarbon group, or C1 to C40
Is a phosphorus-containing hydrocarbon group. R ¹ , R ² and R
³ is a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, respectively. a is 0 or 1. b, c and d are 0≦b≦5 and 0≦c≦ when a is 0, respectively.
5, 0≦d≦5, when a=1, 0≦b≦4, 0≦c
An integer that satisfies ≦4 and 0≦d≦4. X and Y
Are hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group,
Phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom
20 silicon-containing hydrocarbon groups. Me is titanium, zirconium or hafnium. ] 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 the α-olefin. 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.