JPH07292019A - Olefin polymerization catalyst and process for producing olefin polymer - Google Patents

Abstract

(57) [Summary] [Object] To provide a catalyst and a polymerization method for olefin polymerization, which can provide a polyolefin with good particle properties in a high yield without using expensive methylalumoxane. [Structure] An olefin polymerization catalyst, characterized in that the following components A and B are supported on component C, and an olefin characterized by polymerizing by contacting olefin with the catalyst. Polymerization method. A: IVB to VIB having at least one conjugated five-membered ring ligand
Group transition metal compound B: (i) Reaction product of organic Al compound and (ii) R ¹ B (OH) ₂ (R ¹ is a C _{1 to} C ₁₀ hydrocarbon compound, or a halogen-containing hydrocarbon compound) C : Fine particle carrier

Description

Detailed Description of the Invention

BACKGROUND 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, when applied to the polymerization of olefins, exhibits high activity without the use of expensive methylalumoxane, and makes it possible to produce a polymer having good particle properties. The present invention relates to a catalyst and a method for producing an olefin polymer using the catalyst.

[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.

Further, Japanese Patent Laid-Open Nos. 63-92621 and W
In each of O88-05058 publications, it is proposed to support a catalyst component on polyethylene particles. These techniques have enabled the production of a granular polymer even in the case of gas phase polymerization, but as far as the inventors of the present invention know, the activity per carrier is insufficient and the carrier remains in the product. There is a problem because the quality is deteriorated and a large amount of expensive methylalumoxane is used.

On the other hand, as a technique which does not use expensive alumoxane, Japanese Patent Publication Nos. 1-501950 and 1-50203.
No. 6, JP-A-3-179005, and JP-A-3-207703.
No. 3,207,704, anionic compounds represented by organoboron compounds, for example, Lewis acids represented by tris (pentafluorophenyl) boron, carborane, and tetrakis (pentafluorophenyl) borate. There has been proposed a catalyst to be used, or further to use an organic boron compound and a trialkylaluminum together. In addition, JP-A-3-234709,
4-142306, 5-148316, 5-
No. 239138 and No. 5-247128 propose a catalyst system supporting an organoboron-based promoter. However, to the inventors' knowledge, these catalyst systems cause a marked decrease in activity as compared to systems without a carrier, so that despite the absence of methylalumoxane, the cost-cutting effect is low, Further, since the activity per carrier is insufficient, improvement is desired.

[0006]

The present invention has been made in order to solve the problems of the prior art as described above, and has good particle properties even when applied to slurry polymerization or gas phase polymerization. And a method for producing an olefin polymer using such a catalyst, as well as providing a catalyst capable of producing a high polymer in a high yield without using expensive methylalumoxane. The purpose is.

[0007]

[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 olefin polymerization catalyst according to the present invention is characterized in that the following component (A) and component (B) are supported on component (C).

Component (A): Group IVB to VIB transition metal compound having at least one conjugated five-membered ring ligand Component (B): (i) Organoaluminum compound and (ii) R ¹ B
Reaction product with (OH) ₂ (wherein R ¹ has 1 to 10 carbon atoms)
Hydrocarbon Compound or Halogen-Containing Hydrocarbon Compound) Component (C): Fine Particle Carrier The present invention also proposes a method for producing an olefin polymer using the above catalyst. <Effect> The present invention makes it possible to provide a polyolefin having a good particle property in a high yield without using expensive methylalumoxane. It is understood that such an effect is completely unpredictable from the related art. [Detailed Description of the Invention] [Catalyst] The catalyst of the present invention comprises a component (A) and a component (B).
Is obtained by making the component (C) support it. Here, "the product obtained by supporting the component (A) and the component (B) on the component (C)" means that the component (A) and the component (B) are additionally added to the other purpose. And those obtained by supporting the component (C) in the coexistence of various components. Moreover, "supporting" shall include impregnation. <Component (A)> The component (A) of the present invention is a group IVB to VIB transition metal compound of the periodic table having at least one conjugated five-membered ring. Specifically, the following general formula (I) or (I
There are transition metal compounds represented by I).

Q _a (C ₅ H _5-ab R ³ _b ) (C ₅ H _5-ac R ⁴ _c ) MeXY ... (I) S _a (C ₅ H _5-ad R ⁵ _d ) ZMeXY ... (II) 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. Specific examples of Q and S include (a) methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group and other C _{1 to} C ₄ alkylene groups or cyclohexylene groups, or the side thereof. Chain lower alkyl or phenyl substitution product, (b) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisililene group or other silylene group or oligosilylene group or side chain lower alkyl or Phenyl-substituted compounds, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, that is, a hydrocarbon group excluding the divalent valences of these elements required as a bridging group, preferably a lower alkyl group or phenyl Group, or hydrocarbyloxy , Preferably lower alkoxy groups, in particular _{(CH 3)} 2 Ge 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 and the like. Preferred are alkylene groups and silylene groups. a is 0 or 1. The length of Q and S as a bridging group is preferably relatively short, and specifically, for example, 1 to 3
Atoms, preferably 1-2 atoms, are suitable. In this case, the cycloalkylene group and the phenylene group are counted as one atom. Therefore, the preferred Q and S are
For example, methylene group (1 atom), isopropylene group (1
Atom), ethylene group (2 atoms) silylene group (1 atom),
Dimethylsilylene group (1 atom) and disilylene group (2
Atom).

In the above general formula, (C ₅ H _5-ab R ³
_b ), (C ₅ H _5-ac R ⁴ _c ) and (C ₅ H _5-ad R
^The conjugated five-membered ring ligand represented by ⁵ _d ) is defined separately, but b, c and d, and R ³ , R ⁴ and R ⁵ are the same in definition (details below). ), And these 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)
In the case of having a substituent, one specific example of R ³ (or R ⁴ , R ⁵ ) is a hydrocarbon group (C _1- ).
2 C _20, and preferably is C ₁ -C _12), the hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, and this is its neighbor when there are a plurality May be bonded at the other ends thereof to form a ring together with a part of the cyclopentadienyl group. A typical example of the latter is one in which R ³ (or R ⁴ , R ⁵ ) shares a double bond of the cyclopentadienyl group to form a condensed 6-membered ring, that is, this conjugated 5-membered ring group is It 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 ³ , R ⁴ and R ⁵ are each a C _{1 to} C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon group as well as 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) 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 ³ (or R ⁴ , R ⁵ ) is present in plural, they may be the same or different.

B, c and d are 0≤b when a is 0.
≦ 5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, and when a is 1, 0 ≦
It is an integer that satisfies 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-),
Alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10, thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12, silicon-containing hydrocarbon having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group having 1 to 40 carbon atoms, preferably 1 to
18, a nitrogen-containing hydrocarbon group and a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms.

X and Y are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Group having 1 to 20 carbon atoms, preferably 1 to 1
2, a phosphorus-containing hydrocarbon group (specifically, for example, diphenylphosphine group) or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 (specifically, for example, trimethylsilyl group). is there. 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 compound having no conjugated bridging group and two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride, (2) bis (methylcyclo) Pentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6) Bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) Bis (n-butylcyclopentadienyl) zirconium dichloride, (8) Bis (t-butylcyclopentadienyl) zirconium dichloride, (9) Bis (indenyl) zirconium dichloride, (10) Bis (fluorenyl) zirconium Dichloride, (11) bis (cyclopentadienyl) zirconium monochloride monohydride, (12) bis (cyclopentadienyl) methylzirconium monochloride, (13) bis (cyclopentadienyl) ethylzirconium monochloride, (14) ) Bis (cyclopentadienyl) phenyl zirconium monochloride, (15) Bis (cyclopentadienyl) zirconium dimethyl, (16) Bis (cyclopentadienyl)
Zirconium diphenyl, (17) bis (cyclopentadienyl) zirconium dineopentyl, (18) bis (cyclopentadienyl) zirconium dihydride, (1
9) (Cyclopentadienyl) (indenyl) zirconium dichloride, (20) (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-dimethyl) Indenyl) zirconium dichloride, (12) ethylenebis (2
-Methyl-4-trimethylsilylindenyl) zirconium dichloride (13) ethylenebis (2,4-dimethyl-5,6,7-trihydroindenyl) zirconium dichloride, (14) ethylene (2,4-dimethylcyclopentadiene (Enyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (15) ethylene (2
-Methyl-4-tertbutylcyclopentadienyl)
(3'-tertbutyl-5'-methylcyclopentadienyl) zirconium dichloride, (16) ethylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-Trimethylcyclopentadienyl) zirconium dichloride, (17) Isopropylidenebis (2-methylindenyl) zirconium dichloride
(18) Isopropylidene bis (indenyl) zirconium dichloride, (19) Isopropylidene bis (2,4-
Dimethylindenyl) zirconium dichloride, (20)
Isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, (21) isopropylidene (2
-Methyl-4-tertbutylcyclopentadienyl)
(3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (23) methylene (cyclopenta (Dienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (24)
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (25)
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (26)
Methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (27) Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (28) Isopropylidene (cyclopentadienyl) ( 3,4-dimethylcyclopentadienyl) zirconium dichloride,
(29) Isopropylidene (cyclopentadienyl)
(2,3,4,5-Tetramethylcyclopentadienyl) zirconium dichloride, (30) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (31) isopropylidene (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, (32) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (33) isopropylidene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, (32) 34) Isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (35) Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride , (36) Ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (37) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (38) ethylene (2,5-dimethylcyclopentadiene (Enyl) (fluorenyl) zirconium dichloride, (39) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (40) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) ) Zirconium dichloride, (41) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (42) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (43) Shiku Hexylidene (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-methyl-4,4)
4-dimethyl-4,5,6,7-tetrahydro-4-silylindenyl) zirconium dichloride, (4) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (5) dimethylsilylenebis (2-methyl-4,4) 5-benzoindenyl) zirconium dichloride, (6) dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (7) dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, (8) Dimethyl silylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (9) phenylmethylsilylene bis (indenyl)
Zirconium dichloride, (10) Phenylmethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (11) Phenylmethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride (12) Phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (13) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethylcyclopentadienyl) zirconium dichloride, (14) phenylmethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, (15) diphenylsilylene bis (2,4-dimethylindenyl) zirconium dichloride (16) Diphenylsilyl Nbisu (indenyl) zirconium dichloride, (17) diphenyl silylene-bis (2-methylindenyl) zirconium dichloride (18) diphenylsilylene bis (2-methyl-4-
(Phenylindenyl) zirconium dichloride (19) Tetramethyldisililen bis (indenyl) zirconium dichloride, (20) Tetramethyldisilirene bis (cyclopentadienyl) zirconium dichloride, (21) Tetramethyldisilirene (3-methylcyclopenta) (Dienyl) (indenyl) zirconium dichloride, (22) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (23) dimethylsilylene (cyclopentadienyl)
(Trimethylcyclopentadienyl) zirconium dichloride, (24) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (25) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclo Pentadienyl)
Zirconium dichloride, (26) Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (27) Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (28) Dimethylsilylene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, (29) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (30) dimethylsilylene (cyclopentadienyl) ) (Octahydrofluorenyl) zirconium dichloride, (31) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (32) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (33) Dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, (34) Dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (35) Dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (36) Diethylsilylene (2-methylcyclopenta) Dienyl) (2,7-di-
t-Butylfluorenyl) zirconium dichloride, (3
7) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (38) dimethylsilylene (2-
Ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (39) dimethylsilylene (diethylcyclopentadienyl) (2,
7-di-t-butylfluorenyl) zirconium dichloride, (40) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (41) dimethylsilylene (dimethylcyclopentadienyl) (octa Hydrofluorenyl) zirconium dichloride, (42) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (43) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium Dichloride etc.

(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) Ethylboranobis (indenyl) zirconium dichloride, (7) Phenylaminobis (indenyl) zirconium dichloride, (8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride, etc. are exemplified.

(E) Transition metal compounds having one 5-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) amidozirconium dichloride, (2) indenyl-bis (phenyl) amidozirconium Dichloride,
(3) Pentamethylcyclopentadienyl-bis (trimethylsilyl) amide zirconium dichloride, (4)
Pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) dimethylsilylene (tetramethylcyclopentadienyl) (t-butylamide) zirconium dichloride, (6) dimethylsilylene (tetramethylcyclopentadienyl) phenylamide zirconium dichloride, ( 7) dimethylsilylene (tetrahydroindenyl) decylamide zirconium dichloride,
(8) Dimethylsilylene (tetrahydroindenyl)
Examples include (bis (trimethylsilyl) amido) zirconium dichloride, (9) dimethylgermane (tetramethylcyclopentadienyl) phenylamide zirconium dichloride, and the like.

(F) Further, it is also possible to use the compounds of (a) to (e) in which chlorine is replaced by 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 transition metal component, component (B), is changed from zirconium to titanium, hafnium, niobium, molybdenum, tungsten or the like. Other compounds can also be used.

Of these, zirconium compounds, hafnium compounds and titanium compounds are preferable. Even more preferred are titanium compounds, zirconium compounds and hafnium compounds crosslinked with alkylene or silylene groups. <Component (B)> The component (B) is a reaction product of an organoaluminum compound (component (i)) and an alkylboronic acid (component (ii)). (1) Component (i) Component (i) is an organoaluminum compound.

[0027] Component Preferred examples of the organic aluminum compound (i) has the general formula ^{R 2} ₃ Al or ^(R 2)
^{_{2 -Al-O-Al- (R}} 2) is those represented by ₂ (wherein, ^{R 2} is hydrogen, halogen, siloxy group, lower alkylene (about Cl to 6) bridge siloxy group or having 1 to 10 carbon atoms It is a hydrocarbon residue, and a plurality of R ^2's may be the same or different, provided that 3 or 4 R's are present.
Of the ^two , at least one is a hydrocarbon residue having 1 to 10 carbon atoms).

Specifically, (a) trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tri n-butyl aluminum, tri n-propyl aluminum, triisoprenyl aluminum, etc. Of trialkylaluminium,
(B) Alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride,
(C) Alkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride,
(D) Dimethyl aluminum (trimethylsiloxide), dimethyl aluminum (triethyl siloxide), diethyl aluminum (trimethyl siloxide)
And alkyl aluminum siloxides, and (e) tetraalkyl alumoxane such as tetraisobutyl alumoxane and tetraethyl alumoxane. It is also possible to use a mixture of a plurality of these.

Among these organoaluminum compounds, preferred are derivatives of methylaluminum, ethylaluminum and isobutylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diisobutylaluminum chloride and diisobutylaluminum hydride. . More preferable is
Trimethylaluminum, triethylaluminum, triisobutylaluminum, and mixtures thereof. (2) Component (ii) Component (ii) is an alkylboronic acid represented by the general formula R ¹ B (OH) ₂ (R ¹ is a hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms). Represents a residue). Specific examples of such an alkylboronic acid include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, iso-butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid,
Examples include phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, preferable are methylboronic acid, ethylboronic acid, n-butylboronic acid, iso-butylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and the like. More preferred are methylboronic acid, ethylboronic acid, n
-Butylboronic acid and isobutylboronic acid. (3) Contact between component (i) and component (ii) The reaction ratio of component (i) and component (ii) is optional, but the molar ratio of component (i) and component (ii) is 10/1 to 1
/ 10, preferably 4/1 to 1/4, particularly preferably 2
It is preferable to set it to / 1. Also, the component (i)
And the catalytic reaction of component (ii) is usually carried out in an inert solvent under an inert gas atmosphere. Various contact methods can be used. For example, (i) the component (i
Method of mixing i) and then adding dropwise a diluted solution of component (i) in toluene to react, (b) Method of supplying component (ii) as a solid in a solution of component (i) diluted with hexane and reacting ,
(C) A method of diluting the component (i) and the component (ii) in toluene and dropping each of them at a constant rate into another container to react them is exemplified. The reaction temperature and reaction time of the component (i) and the component (ii) are arbitrary, but in general, both components are low temperature, for example, -78 to 30 ° C, preferably- After mixing at 78 to 10 ° C, a method of gradually raising the temperature, for example, -10 to 70 ° C is preferable. The reaction time is arbitrary as long as the desired product is obtained, but it is generally carried out in the range of 1 minute to 24 hours. <Component (C)> The component (C) is a fine particle carrier. The fine particle carrier may be either organic or inorganic. As the organic compound carrier, (a) α-olefin polymer, for example, polyethylene, polypropylene, polybutene-1,
Ethylene-propylene copolymer, ethylene-butene-1
Copolymers, ethylene / hexene-1 copolymers, propylene-butene-1 copolymers, propylene-hexene-1 copolymers, propylene-divinylbenzene copolymers, etc.
(B) Aromatic unsaturated hydrocarbon polymers such as polystyrene, styrene-divinylbenzene copolymer and the like and (c) Polar group-containing polymers such as polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, polyvinyl chloride. , Known as polyamides, polyphenylene ethers, polyethylene terephthalates, polycarbonates, and ion exchange resins,
Etc. are illustrated. Examples of the inorganic carrier include (a) inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
_{2, SiO 2 -MgO, SiO 2} -Al 2 O 3, SiO
_{2 -TiO 2, SiO 2 -V 2} O 5, SiO 2 -Cr 2
O _{3, SiO 2} -TiO 2 -MgO, etc., (b) inorganic halides such as MgCl _2, AlCl _3, MnCl ₂
(C) Inorganic carbonates, sulfates or nitrates such as Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (N
( ₃ ) ₂ etc., and (d) inorganic hydroxides such as Mg (O)
H) ₂ , Al (OH) ₃ , Ca (OH) _{2 and the} like are exemplified.

These carriers are usually 0.006 to 10 μm.
The volume of the pores of m is 0.1 cc / g or more, preferably 0.
Those existing at 3 cc / g or more, more preferably 0.8 cc / g or more are used. Especially 0.05 to 2 μm
It is effective that the sum of the volume of the pores present in 1) is 50% or more of the total volume of the pores in the range of 0.006 to 10 μm.

Since this carrier is a "particulate carrier", its particle size should be sufficiently small.
The preferred particle size is generally 1 to 3000 μm, preferably 5 to 2000 μm, and more preferably 10 μm to 10.
The range is 00 μm. <Arbitrary component> The catalyst of the present invention can be obtained by supporting the above-mentioned components (A) and (B) on the component (C), but any component may be used as long as the effect is not impaired. Is possible. Examples of the optional component that can be added include active hydrogen-containing compounds such as H ₂ O, methanol, ethanol, butanol, ethers, esters,
Electron-donating compounds such as amines, phenyl borate, dimethyl methoxyaluminum, phenyl phosphite, tetraethoxysilane, alkoxy-containing compounds such as diphenyldimethoxysilane, triethylborane, triphenylborane, tris (pentafluorophenyl) borane, tri Phenylcarbyl tetrakis (pentafluorophenyl)
Examples thereof include organic boron compounds such as borane. <Preparation of catalyst> The catalyst of the present invention can be obtained by supporting the component (A) and the component (B) on the component (C). The method of supporting the component (A) and the component (B) on the component (C) is optional, and it has been described above that "impregnation" is included, but in general, the component (A) and the component (A) (B) a method in which (B) is dissolved in an insoluble solvent capable of dissolving the respective components, mixed with the component (C), and then the solvent is distilled off under reduced pressure or under an inert gas stream;
After the components (A) and (B) are dissolved, the components are concentrated within a range where solids do not precipitate, and then the component (C) is added in an amount capable of keeping the total amount of the concentrated liquid in the particles. Method (C) in which component (B) is supported, and then a diluting solution of component (A) in an inert solvent is added dropwise, (d) component (A)
Is supported on the component (C), and then a diluting solution of the component (B) in an inert solvent is added dropwise.

Since the component (A) of the present invention is generally a solid and the component (B) has a pyrophoric property, both of them may be diluted with an inert solvent before use. Examples of the inert solvent used for this purpose include benzene, toluene, xylene, hexane, heptane, octane, decalin, dichloromethane, dichloroethane, chloropropane and chlorobenzene.

The amount of each component used is arbitrary, but in view of activity or economy, generally, the amount of the compound of the component (A) used is 0.00001 to 1 gram of the component (C).
1 gram, preferably 0.0001 to 0.1 gram, more preferably 0.0005 to 0.05 gram. The amount of the component (B) used is 0.0001 to 10 crumb, preferably 0.00, to 1 gram of the component (C).
It is 1 to 5 grams, more preferably 0.005 to 2 grams. Further, the atomic ratio of the transition metal (M) of the component (A) to the Al of the component (B) is 1: 0.1 to 1: 100,000.
It is used in the range of 0, preferably 1: 1 to 1 to 10,000, more preferably 3: 3,000.

The component (A), the component (B) and the component (C) obtained above may be contacted with an olefin and subjected to a preliminary polymerization which comprises polymerizing a small amount of the olefin. It is possible. Preliminary polymerization is generally carried out by a slurry polymerization method carried out in an inert solvent or a gas phase polymerization method carried out under gas phase conditions. The monomers used at that time are ethylene, propylene, butene-1, 3
-Methylbutene-1,4-methylpentene-1, hexene-1, styrene, divinylbenzene or mixtures thereof are preferred. If necessary, hydrogen can be used together to control the molecular weight, and an inert gas such as nitrogen can be used together to control the reaction. Pre-polymerization is −78 ° C.-100
C., preferably in the range of −78 ° C. to 50 ° C. The prepolymerization time is 1 minute to 24 hours, preferably 5 minutes to 10
The amount of prepolymerization is 0.01 to 500 g, preferably 0.05 to 500 g per 1 g of the solid component.
100 grams, more preferably 0.1-30 grams,
Is the range. The prepolymerization is usually carried out under conditions milder than the main polymerization in terms of temperature and / or pressure. <Olefin Polymerization> The catalyst of the present invention is, of course, applied to solvent polymerization using a solvent, but is also applied to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially without using a solvent. It It is also applied to continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, hexane, heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbon solvents such as toluene may be used alone or as a mixture.

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 normal pressure to 50 kg / c.
It is in the range of m 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.

The olefin polymerized by the catalyst of the present invention (including ethylene in the present invention), that is, the olefin used in the polymerization reaction in the method of the present invention has 2 carbon atoms.
-20, preferably 2-10 alpha-olefins. 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 and the like, particularly preferably ethylene, propylene, 1-
There are butenes, 1-hexene and 4-methyl-1-pentene. These α-olefins may be mixed for use in polymerization.

Further, the catalyst of the present invention can also be copolymerized with the above-mentioned olefins and ethylene. Furthermore, the above α
-Other monomers copolymerizable with olefins, such as butadiene, 1,4-hexadiene, 1,8-nonadiene, 7
For the copolymerization of conjugated and non-conjugated dienes such as -methyl-1,6-octadiene and 1,9-decadiene, or cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene and dicyclopentadiene. It is valid.

Needless to say, the catalyst of the present invention comprising such components (A) to (C) can be polymerized by itself, but if necessary, for example, to prevent poisoning of the solvent or the reaction system. Therefore, it is also possible to use organoaluminum as an additional component in the coexistence during the polymerization. Specific preferred examples of the organoaluminum compound include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and other trialkylaluminums, (b) diethylaluminum monochloride, diisobutylaluminum. Alkyl aluminum halides such as monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) diethyl aluminum hydride, alkyl aluminum hydrides such as diisobutyl aluminum hydride, (d) diethyl aluminum ethoxide, dimethyl aluminum trimethylsiloxide, diethyl aluminum phenoxide Such as aluminum Rukokishido, (e) methyl alumoxane, ethyl alumoxane, isobutyl alumoxane, such as alumoxane, such as methyl isobutyl alumoxane are exemplified. It is also possible to use a mixture of a plurality of these.
Of these, trialkylaluminum and aluminum alkoxide are preferable. More preferred are organoaluminum compounds having a methyl group, an ethyl group, and an isobutyl group.

[0040]

【Example】

<Example-1> (1) Production of catalyst component (A) Dimethylsilylbis (tetrahydroindenyl) zirconium dichloride was added to J. Orgmet. Chem. (342) 21-29.
1988 and J. Orgmet. Chem. (369) 359-370 1989 .

Concretely, 5.4 g of bis (indenyl) dimethylsilane was diluted to 150 ml of tetrahydrofuran in a 300 ml flask purged with nitrogen, cooled to -50 ° C. or lower, and then n-butyllithium (1.6M). / L) of 23.6 ml 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.
Zirconium tetrachloride 4.38 after cooling below 50 ° C
Grams were introduced slowly. 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 the solvent was distilled off again to obtain 3.86 g of crude dimethylsilylbis (indenyl) zirconium dichloride crystals.

Then, the crude crystals were mixed with dichloromethane 15
It was dissolved in 0 ml and introduced into a 500 ml autoclave, and after introducing 5 g of a platinum-carbon (0.5 wt% platinum supported) catalyst, H ₂ = 50 kg / cm ² G,
The hydrogenation reaction was carried out at 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. (2) Manufacture of component (B) 5 equipped with a stirrer and a reflux condenser with sufficient nitrogen substitution
100 ml of dehydrated and deoxygenated toluene was introduced into a 00 ml flask. Then, 2.04 g (20 mmol) of n-butylboronic acid was introduced and the temperature was -50 ° C.
Cooled to: Then triisobutylaluminum 3
0 mmol and 10 mmol of triethylaluminum were mixed and diluted with 100 ml of toluene and added dropwise with a dropping funnel over 30 minutes. After the dropping was completed, the reaction temperature was slowly raised over 3 hours. Evolution of gas was observed in the range of -20 ° C to -5 ° C. After the temperature was raised to 20 ° C., the reaction was terminated by further stirring for 2 hours to obtain the target component (B). This solution contained 0.2 mM of aluminum atom / cc. (3) Production of solid catalyst As component (C), porous polypropylene powder manufactured by Akzo (trade name; “Accurel” 200 to 400 μm)
m classification product) was used. Pore size of this powder 0.05
The pore volume between μ and 2.0 μ is 1.89 cc / g, 0.
The total pore volume between 006μ and 10μ is 2.54cc / g
Met.

In a 300 ml flask sufficiently replaced with nitrogen, 10 g of the above-mentioned porous polypropylene (200 μ or less) manufactured by Akzo Co. as the component (i), the component (B) obtained above was 9 mmol in terms of Al atom, And ingredient (A)
Was introduced in an amount of 90 μmol. After the introduction, the solvent toluene was stirred and dried under a nitrogen stream for 2 hours to obtain 16.6 g of a target solid catalyst. (4) Polymerization of ethylene After introducing 80 g of fully dehydrated and nitrogen-substituted sodium chloride into a stirring type autoclave having an internal volume of 1.5 liters, the temperature of the autoclave was raised to 60 ° C and replaced with ethylene. Then 1 gram of the solid catalyst obtained above (component (A)
2.45 mg) and then introduce 50 cc of hydrogen to 70
The reaction was carried out at an ethylene pressure of 7 kg / cm ² G for 2 hours. After the completion of the reaction, the solid was recovered, washed with a large amount of water to remove sodium chloride, and then dried. As a result, 35 g of a polymer was recovered. Bulk density is 0.36 g / cc, MI (190
C.) = 5.6 g / 10 min, activity per component (A) is 1
It was 4,300 g polyethylene / g component (A). <Example-2> (1) Production of solid catalyst 5 g of the solid catalyst obtained in Example-1 was replaced with nitrogen 50
The mixture was divided into 0 ml flasks, and vapor phase prepolymerization was carried out for 30 minutes under atmospheric pressure while flowing a mixed gas of ethylene and nitrogen while cooling the flask with ice water. At this time, the feed rate of the mixed gas was adjusted so that the internal temperature did not exceed 30 ° C. After the completion of prepolymerization,
As a result of measuring the whole weight, it was 17.4 g.
Therefore, 14.20 g polyethylene / component (A)
It was the g component (A). (2) Polymerization of ethylene Polymerization was carried out under the same conditions as in Example-1, except that 2 g of the prepolymerized catalyst obtained above was used. The results are shown in Table-1.
As shown in. <Examples 3 and 4> (1) Polymerization of ethylene Polymerization was carried out in the same manner as in Example 1 or 2 except that 100 mg of triisobutylaluminum was added as an additional component during the polymerization of Examples 1 and 2. I did.
The results are as shown in Table-1. <Example-5> (1) Polymerization of ethylene Into a 1.5-liter stirring autoclave, 500 ml of sufficiently dehydrated and degassed toluene was introduced,
After replacing with ethylene, add 1 part of triisobutylaluminum.
45 mg was introduced. After raising the temperature to 60 ° C,
1 g of the prepolymerized catalyst component obtained in Example 2 was introduced, and then 50 cc of hydrogen was added, and then ethylene pressure was adjusted to 7 at 70 ° C.
Polymerization was performed for 2 hours at kg / cm ² G. The results are as shown in Table-1. <Example-6> (1) Production of solid catalyst Ion exchange resin C manufactured by Nippon Rensui Co., Ltd. as component (C)
RB-02 was used. That is, except that 10 g of anhydrous CRB-02 obtained by performing a reduced pressure drying treatment to wash away the contained water by thoroughly washing with acetone and using the same procedure as in Example-1 were used. A solid catalyst was produced. The particle size of CRB-02 is 350-550
μm. As a result, 1 g of the obtained solid catalyst contained 2.60 mg of the component (A). (2) Polymerization of ethylene Polymerization was carried out under the same conditions as in Example-3 except that 2 g of the solid catalyst obtained above was used. The results are shown in Table-1
Shown in. <Examples 7 to 10> (1) Production of component (B) In producing the component (B) of Example-1, the component (i) and the component
The same procedure as in Example-1 was carried out except that (ii) was changed as shown in Table-2. (2) Production of solid catalyst and polymerization of ethylene A solid catalyst was produced under the same conditions as in Example-1, except that the component (B) obtained above was used, and ethylene was further polymerized. The results are shown in Table-2. <Comparative Examples-1 and 2> (1) Production of solid catalyst In Example-1, instead of the component (B), 9 mmol of triisobutylaluminum was used, or
Example 1 except that 9 mmol of triisobutylaluminum and 180 μmol of (dimethylanilinium) tetrakispentafluorophenyl) borate were used.
A solid catalyst was synthesized under the same conditions as above. The results are shown in Table-2. <Example-11> (1) Copolymerization of ethylene / 1-hexene Using 1 gram of the solid catalyst obtained in Example-2, 30 ml of 1-hexene was added, and all were used as in Example-5 except that hydrogen was not used. Polymerization operation was performed under the same conditions. As a result, 35.5 grams of polymer was recovered. The MI (190 ° C.) of this polymer is 23.5 g / 10 minutes,
The melting point of the polymer was 112.0 ° C. <Example-12> (1) Polymerization of propylene After thoroughly stirring a stirring autoclave having an internal volume of 1.2 liters with propylene, 500 ml of propylene was introduced. Then, 1 gram of the catalyst obtained in Example-1 was introduced by pressurizing with argon, then the temperature was raised to 70 ° C. and a polymerization operation was performed for 2 hours. After the polymerization was completed, the propylene monomer was purged, and as a result, 85.5 g of the polymer was recovered. Therefore, the catalytic activity is 34900 g polypropylene /
g component (A), and the melting point of the polymer was 128.5 ° C. <Example-13> (1) Production of solid catalyst "Silica 948" (average particle diameter 50 µm, pore volume 1.66 cc / g) manufactured by Devison was used as a component (C).

Into a 300 ml flask which had been sufficiently replaced with nitrogen, 4 parts of the above-mentioned silica manufactured by Devison Co. was used as the component (C).
32 g of the component (B) obtained above in terms of Al atom, and 30 μmol of bis (n-butylcyclopentadienyl) zirconium dichloride were introduced. After the introduction, the solvent toluene was stirred and dried under a nitrogen stream to obtain 7.1 g of a target solid catalyst. (2) Polymerization of ethylene The polymerization was carried out in the same manner as in Example 5, except that 1.0 g of the above solid catalyst component was used. As a result, 81.5 g of polymer was obtained. The activity per component (A) is 47,
It was 700 (g polyethylene / g component (A)), the bulk density was 0.38 g / cc, and MI = 1.1 (g / 10 minutes).

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

INDUSTRIAL APPLICABILITY The present invention makes it possible to provide a polyolefin having a good particle property in a high yield without using expensive methylalumoxane.
It has been described above in the [Summary of Invention] section.

Front page continuation (72) Inventor Tomohiko Takahama 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (6)

[Claims] 1. A catalyst for olefin polymerization, comprising the following component (A) and component (B) supported on component (C). Component (A): IV having at least one conjugated five-membered ring ligand IV
Group B-VIB transition metal compound Component (B): (i) Organoaluminum compound and (ii) R ¹ B
Reaction product with (OH) ₂ (wherein R ¹ has 1 to 10 carbon atoms)
Hydrocarbon Compound or Halogen-Containing Hydrocarbon Compound) Component (C): Fine Particle Carrier 2. The catalyst for olefin polymerization according to claim 1, wherein the component (A) is represented by the following general formula (I) or (II). _{Q a (C 5 H 5-} ab R 3 b) (C 5 H 5-ac R 4 c) MeXY ... (I) S a (C 5 H 5-ad R 5 d) ZMeXY ......... (II) [ Q is a bonding group bridging the two conjugated five-membered ring ligands, S is a bonding group bridging the conjugated five-membered ring ligand and the Z group, and R ^{3 to} R ⁵ are respectively Independently, 1-2 carbon atoms
0 is a hydrocarbon group, 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, and Me is a periodic table.
IVB to VIB group transition metal, Z is oxygen (-O-), sulfur (-S-), a C1-C20 alkoxy group, a C1-C20 thioalkoxy group, a C1-C40. X is a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms.
And Y are each independently hydrogen, a halogen group, or a carbon number of 1.
~ 20 hydrocarbon groups, C1-20 alkoxy groups,
An amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms (specifically, for example, a diphenylphosphine group), or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and a is a number of 0 or 1, b to d are 0 ≦ b ≦ 5, 0 when a is 0.
≦ c ≦ 5, 0 ≦ d ≦ 5, when a is 1, 0 ≦ b ≦
4, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, respectively] 3. The component (B) comprises (i) an organoaluminum compound represented by the following general formula (III) or (IV):
i) methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, i
selected from so-butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl) phenylboronic acid The catalyst for olefin polymerization according to claim 1, which is a reaction product with an alkylboronic acid. _{^{R 2 3 Al ...... (III)}} (R 2) 2 -Al-O-Al- (R 2) 2 ...... (IV) ^{[R 2} is hydrogen, halogen, a siloxy group, a carbon number 1 to 6
Is an alkylene-bridged siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and a plurality of R ² may be the same or different, provided that at least one of 3 or 4 R ² is carbon. It is a hydrocarbon residue of the number 1 to 10] 4. Component (C) is (a) polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, propylene-butene. -1 copolymer, propylene-hexene-1 copolymer, propylene-
Α-olefin polymers selected from divinylbenzene copolymers, (b) polystyrene, aromatic unsaturated hydrocarbon polymers such as styrene-divinylbenzene copolymers, (c)
Polyacrylic acid ester, polymethacrylic acid ester,
Polyacrylonitrile, polyvinyl chloride, polyamide,
Polar group-containing polymer selected from polyphenylene ether, polyethylene terephthalate, and polycarbonate,
(C) SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti
O ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ,
SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO _2-
TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr
₂ O ₃ , inorganic oxide selected from SiO ₂ —TiO ₂ —MgO, (d) inorganic halide selected from MgCl ₂ , AlCl ₃ and MnCl ₂ , (e) Na ₂ CO ₃ , K
₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al ₂ (SO ₄ )
Inorganic carbonate, sulfate or nitrate selected from ₃ , BaSO ₄ , KNO ₃ and Mg (NO ₃ ) ₂ , or (f)
The olefin polymerization catalyst according to any one of claims 1 to 3, which is an inorganic hydroxide selected from Mg (OH) ₂ , Al (OH) ₃ , and Ca (OH) ₂ . 5. The component (C) has a particle size of 1 to 3000 μm.
And the sum of the volumes of the pores present in the pore diameter of 0.05 to 2 μm is 50% or more of the total of the pore volumes of all the pores present in the range of 0.006 to 10 μm. The olefin polymerization catalyst according to any one of claims 1 to 4. 6. A process for producing an olefin polymer, which comprises contacting an olefin with the catalyst for olefin polymerization according to any one of claims 1 to 5 for polymerization.