JPH08291203A - Catalyst for olefinic polymerization and production of olefinic polymer by using the same - Google Patents

Abstract

PURPOSE: To obtain the subject catalyst consisting of a transition metal compound, an organoaluminum compound and a composition of fine particles, not using an expensive methyl alminoxane, and capable of obtaining a polyolefin having a good particle properties in a high yield. CONSTITUTION: This olefin polymerization catalyst consists of (A) a transition metal compound in the groups 4 to 6 in the periodic table having at least one conjugated 5 membered ring ligand, (B) an organoaluminum compound and (C) (i) a composition of fine particles containing 0.1-99.9wt.% boric acid. Further, it is preferable that the component A is expressed by formula I to formula IV (A, A' are each a conjugated 5 membered ring ligand; Q is a binding group cross-linking the ligands; Z is a ligand containing N, O, etc., binding to Me; Q' is a binding group cross-linking between the ligand and Z; Me is a metallic element in the groups 4 to 6; X, Y are each H, a halogen, etc., binding to Me), the component B is R3 Al (R3 is H, a halogen, a siloxy, etc.) and the component C consists of the fine particle raw material of the component (i) of B(O)n (OH)m-n , (under the condition of n=0, m=3, etc.) and (ii) an α-olefin polymer, etc.

Description

Detailed Description of the Invention

[Background of the Invention]

TECHNICAL FIELD 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 enables the production of a polymer having good particle properties for olefin polymerization. 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 methylalumoxane 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 (JP-A-61-1303).
No. 14, 63-295607, JP-A-1-3017.
No. 04 and No. 2-41303). However, to the present inventors, these proposals enable the production of a polymer having high activity and a narrow molecular weight distribution, but on the other hand, since the catalyst is soluble in the solvent toluene, it has a very small particle size. Only a fine (usually about 1 to 50 μm) polymer can be obtained,
It was difficult to industrially produce a polymer with high efficiency.
Also, this method seems to be costly, as it requires the use of large amounts of alumoxane. Various proposals have been made to solve such problems. JP-A-6
4-51408, JP-A-1-27560 and 3
In each of the publications of -140305, the alumoxane and the metallocene compound are brought into contact with each other in advance to granulate the produced polymer. However, particle formation by this method is limited to so-called liquid phase bulk polymerization using a propylene solvent, and it seems that a polymer having a controlled particle size cannot be obtained by slurry polymerization or gas phase polymerization using an inert solvent. is there.

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 compound, 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 granular polymers 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 as a residue in the product. There is a problem because it causes quality deterioration and uses a large amount of expensive methylalumoxane.

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. However, in the polymerization using these catalysts, only a polymer having a very small particle size can be obtained, and it is difficult to industrially produce the polymer with high efficiency. Further, JP-A-3-179005 and 4-142.
No. 306, No. 5-148316, No. 5-239138
No. 5 and No. 5-247128 propose a catalyst system supporting an organic boron co-catalyst,
The organoboron compound does not contain boric acid, and the inventors of the present invention are aware that the catalyst system supporting these organoboron co-catalysts causes a remarkable decrease in activity as compared with a system without a carrier. Despite not using methylalumoxane, the cost-cutting effect is low, and the activity per carrier is insufficient, so improvement is desired.

As another method, it is proposed to use a combination of a water-containing inorganic compound and an organic aluminum compound (JP-A-1-207303 and 4-224808).
No. 5/501424). However, neither of them seems to have sufficient catalytic activity. Further, JP-A-6-157651 proposes using Bronsted acid, JP-A-5-105721 and JP-A-5-301917.
In the issue, there is a proposal to use clay minerals, but especially in the latter case, there is a problem that clay minerals are special as a carrier and it is difficult to control their properties.

[0007]

The present invention has been made in order to solve the problems of the prior art as described above, and is applied to slurry polymerization or gas phase polymerization without using a special carrier. Even in the case of using the catalyst, it is possible to provide a catalyst that makes it possible to produce a polymer having good particle properties in high yield without using expensive methylalumoxane, and use such a catalyst to produce an olefin polymer. It is intended to be manufactured. [Outline of the Invention]

[0008]

[Means for Solving the Problems]

<Summary> The present invention has been found as a result of intensive studies on the above-mentioned object.

That is, the olefin polymerization catalyst according to the present invention is characterized by comprising the following components (A), (B) and (C). Component (A): Group 4 to 6 transition metal compound having at least one conjugated five-membered ring ligand Component (B): Organoaluminum compound Component (C): 0.1 to 99.9 wt% boron A fine particle composition comprising an acid. <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 for olefin polymerization according to the present invention comprises the component (A), the component (B) and the component (C). Here, the term “consisting of” includes not only the above-mentioned components, that is, the components (A), (B) and (C), but also purposeful components other than these components. It also means that Such an olefin polymerization catalyst according to the present invention can be obtained by contacting the component (A), the component (B) and the component (C) and, if necessary, other components in any order.

When the olefin polymerization catalyst according to the present invention is used for polymerization, the catalyst component can be used in a slurry state or in a previously dried solid state. Further, it is also possible to carry out a prepolymerization which comprises contacting each catalyst component in an arbitrary state and then contacting an olefin to polymerize a small amount of the olefin, followed by use in the polymerization.

<Component (A)> The component (A) of the catalyst for olefin polymerization according to the present invention is a transition metal compound of Groups 4 to 6 of the Periodic Table having at least one conjugated five-membered ring ligand.
Specific examples of preferred compounds as the component (A) include transition metal compounds represented by the following general formulas [I], [II], [III] or [IV].

[0013]

Embedded image [Here, A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Z is a bonding group that bridges at an arbitrary position, Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to Me, and Q ′ is a conjugated five-membered ring system. Me is a metal atom selected from Groups 4 to 6 of the Periodic Table, and X and Y.
Is a hydrogen group bonded to Me, a halogen group, a hydrocarbon group,
An alkoxy group, an amino group, a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group are shown respectively. As described above, A and A ′ are conjugated five-membered ring ligands, which may be the same or different in the same compound. This conjugated five-membered ring ligand (A and A ')
As a typical example of, a conjugated carbon five-membered ring ligand, that is, a cyclopentadienyl group can be mentioned. The cyclopentadienyl group may be one having 5 hydrogen atoms [C ₅ H ₅ −], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with a substituent, May be One specific example of this substituent is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. This hydrocarbon group is bonded as a monovalent group to a cyclopentadienyl group. Also, when a plurality of them are present, two of them may be bonded at the other end (ω-end) to form a ring together with a part of the cyclopentadienyl group. Typical examples of the latter are those in which two substituents are bound at their ω-ends and share two adjacent carbon atoms in the cyclopentadienyl group to form a fused six-membered ring. , That is, an indenyl group or a fluorenyl group.

Therefore, typical examples of the conjugated five-membered ring ligand (A and A ') can be a substituted or unsubstituted cyclopentadienyl group, an indenyl group or a fluorenyl group.

As the substituent on the cyclopentadienyl group, in addition to the aforementioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a halogen group (eg, fluorine, chlorine, bromine), alkoxy group A group (for example, _one of C _{1 to} C ₁₂ ), a silicon-containing hydrocarbon group (for example, a silicon atom in the form of —Si (R ¹ ) (R ² ) (R ³ ), having 1 to carbon atoms.
24 groups), a phosphorus-containing hydrocarbon group (for example, a phosphorus atom in the form of -P (R ¹ ) (R ² ), having 1 to 18 carbon atoms.
Degree group), a nitrogen-containing hydrocarbon group (for example, a group having a nitrogen atom in the form of -N (R ¹ ) (R ² ) and having about 1 to 18 carbon atoms), or a boron-containing hydrocarbon group (for example, a boron atom). Having from 1 to 1 carbon atoms in the form of -B (R ¹ ) (R ² ).
It is a group of about 8). If there are multiple of these substituents,
Each substituent may be the same or different.

Q is a bonding group bridging two conjugated five-membered ring ligands at an arbitrary position, and Q'is a bonding group bridging an arbitrary position of the conjugated five-membered ring ligand to a Z group. Is represented.

Specifically, Q and Q'are (a) an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group, and ) Silylene group, dimethylsilylene group, phenylmethylsilylene group,
Diphenylsilylene group, disilylene group, silylene group such as tetramethyldisililene group, hydrocarbon group containing (iii) germanium, phosphorus, nitrogen, boron or aluminum [specifically, (CH ₃ ) ₂ Ge group, (C ₆ H ₅ ) ₂ G
e 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 ) A group
1 group, (CH ₃ O) Al group, etc.] and the like. Preferred are alkylene groups and silylene groups.

Me is a metal atom selected from Groups 4 to 6 of the Periodic Table, preferably titanium, zirconium and hafnium. Particularly, titanium and zirconium are preferable.

Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to Me. Specific examples of preferable Z include:
Oxygen (-O-), sulfur (-S-), carbon number 1-20,
Preferably, an alkoxy group having 1 to 10 carbon atoms, 1 to 20 carbon atoms,
Preferably 1 to 12 thioalkoxy group, 1 to 4 carbon atoms
0, preferably 1-18 silicon-containing hydrocarbon group, 1-40 carbon atoms, preferably 1-18 nitrogen-containing hydrocarbon group, 1-40 carbon atoms, preferably 1-18 phosphorus-containing hydrocarbon group is there.

X and Y are each 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, 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, halogen groups and hydrocarbon groups (especially those having 1 to 8 carbon atoms)
And amino groups are preferred.

Therefore, among the compounds represented by the general formulas [I], [II], [III] and [IV] which are preferable as the component (A) in the catalyst component for olefin polymerization according to the present invention, particularly preferable ones are It has a substituent of each of the following contents. A, A ′ = cyclopentadienyl, n-butyl-cyclopentadienyl, indenyl, 2-methyl-indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-
Tetrahydroindenyl, 2-methylbenzoindenyl, Q, Q '= ethylene, dimethylsilylene, isopropylidene, Z = t-butylamide, phenylamide, cyclohexylamide, Me = Group 4 transition metal, X, Y = chlorine, methyl , Diethylamino.

In the present invention, the component (A) is within the group of compounds represented by the same general formula, and / or
Among compounds represented by different general formulas, they can be used as a mixture of two or more kinds of compounds.

Specific examples of this transition metal compound when Me is zirconium are as follows. (A) A compound represented by the general formula [I], that is, a transition metal compound having no conjugated group Q and two conjugated five-membered ring ligands, for example, (1) bis (cyclopentadienyl) zirconium Dichloride, (2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetra Methylcyclopentadienyl) zirconium dichloride, (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, ( 11) bis (cyclopentadienyl) methyl zirconium monochloride, (12) bis (cyclopentadienyl) ethyl zirconium monochloride, (13) bis (cyclopentadienyl) phenyl zirconium monochloride, (14) bis (cyclo Pentadienyl) zirconium dimethyl, (15) bis (cyclopentadienyl) zirconium diphenyl, (16) bis (cyclopentadienyl) zirconium dineopentyl, (17) bis (cyclopentadienyl) zirconium dihydride, ( 18) (Cyclopentadienyl (Indenyl) zirconium dichloride, (19) (cyclopentadienyl)
(Fluorenyl) zirconium dichloride and the like.

(B) A compound represented by the general formula [II], that is, a compound having a bonding group Q, for example, (b-1) Q = 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 monomethoxide monochloride, (6) ethylenebis (indenyl) zirconium diethoxide, (7) ethylenebis (indenyl) zirconium Dimethyl, (8) ethylene bis (4,5,6,7-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-tert-butylcyclopentadiene) (Enyl) (3'-tert butyl-5'-methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-Trimethylcyclopentadienyl) zirconium dichloride, (15) ethylene-1,2-
Bis (4-indenyl) zirconium dichloride, (16)
Ethylene-1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride, (17) ethylene-
1,2-Bis (4-phenylindenyl) zirconium dichloride, (18) isopropylidenebis (indenyl)
Zirconium dichloride, (19) isopropylidene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (20) isopropylidene (2-thymer-4-tertbutylcyclopentadienyl) (3'-tertbutyl- 5-methylcyclopentadienyl) zirconium dichloride,
(21) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (23) methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) zirconium dimethyl, (24) methylene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) zirconium diphenyl, (25) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (2
6) Methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (27) Isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (28) Isopropylidene (Cyclopentadienyl)
(2,3,4,5-Tetramethylcyclopentadienyl) zirconium dichloride, (29) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (30) isopropylidene (cyclopentadienyl) ) (Fluorenyl) zirconium dichloride, (31) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(32) isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(33) Isopropylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (34) Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl ) Zirconium dichloride, (35) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (36) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (37) ethylene (2 , 5-Dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
8) Ethylene (2,5-diethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (39) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride,
(40) Diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, (41) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(42) Cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethyldimethylcyclopentadienyl) zirconium dichloride and the like.

(B-2) As Q = silylene group,
For example, (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,
5,6,7-Tetrahydroindenyl) zirconium dichloride, (3) Dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (4) Dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (5) Dimethyl silylene bis (2-methyl-
4,5,6,7-Tetrahydroindenyl) zirconium dichloride, (6) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (7) Dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, (8) Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, (9) Dimethylsilylenebis (2-methyl- 4,4-dimethyl-4,5,6,7-tetrahydro-4-cyraindenyl) zirconium dichloride, (10)
Dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride, (11) Dimethylsilylenebis [4- (2-tertbutylindenyl)] zirconium dichloride, (12) Dimethylsilylenebis [4- (2-
(Phenyl-3-methylindenyl)] zirconium dichloride, (13) phenylmethylsilylene bis (indenyl) zirconium dichloride, (14) phenylmethylsilylene bis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, (15) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-Dimethylcyclopentadienyl) zirconium dichloride, (16) phenylmethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) zirconium dichloride, (17) phenylmethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, (1
8) diphenylsilylene bis (indenyl) zirconium dichloride, (19) tetramethyldisilylene bis (indenyl) zirconium dichloride, (20) tetramethyldisilylene bis (cyclopentadienyl) zirconium dichloride, (21) tetramethyldisilylene ( 3-methylcyclopentadienyl) (indenyl) zirconium dichloride, (22) dimethylsilylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, (23) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (24) dimethylsilylene (cyclopentadienyl) (tetramethylcyclo (Pentadienyl) zirconium dichloride, (25) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (26) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) Zirconium dichloride, (27) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (28) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (29) dimethyl Tillsilylene (3-tert
-Butyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, (30) dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (31) dimethylsilylene (cyclopenta) Dienyl) (octahydrofluorenyl) zirconium dichloride, (32) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (33) dimethyl silylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (34) dimethylsilylene (2-
Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (35) Dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (36) Diethylsilylene (2-methylcyclopentadienyl) (2 ′, 7′-Di-t-butylfluorenyl) zirconium dichloride, (37) 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) (octahydro Fluorenyl) zirconium dichloride, (42) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (43) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride etc.

(B-3) Q = germanium, a hydrocarbon group containing phosphorus, nitrogen, boron or aluminum, for example, (1) dimethylgermanium bis (indenyl) zirconium dichloride, (2) dimethylgermanium (cyclopentadiene) (Enyl) (fluorenyl) zirconium dichloride, (3) methyl aluminum bis (indenyl) zirconium dichloride, (4) phenyl aluminum 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.

(C) a compound represented by the general formula [III],
That is, a transition metal compound having no conjugated group Q ′ and one conjugated five-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride, (2) indenyl-bis (Phenyl) amidozirconium dichloride, (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4) pentamethylcyclopentadienylphenoxyzirconium dichloride and the like.

(D) A compound represented by the general formula [IV], that is, a transition metal compound having one conjugated five-membered ring ligand bridged by a bonding group Q ', such as (1) dimethylsilylene (tetramethyl). Cyclopentadienyl) phenylamide zirconium dichloride, (2) dimethylsilylene (tetramethylcyclopentadienyl) tert-butylamide zirconium dichloride, (3) dimethylsilylene (indenyl) cyclohexylamide zirconium dichloride,
(4) Dimethylsilylene (tetrahydroindenyl) decylamide zirconium dichloride, (5) Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl)
(Amino) zirconium dichloride, (6) dimethylgermane (tetramethylcyclopentadienyl) (phenyl)
Amino zirconium dichloride and the like are exemplified.

(E) Further, it is also possible to use the compounds of the above (a) to (d) 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 (e) as the component (A) is zirconium to titanium, hafnium, niobium,
A compound replacing molybdenum or tungsten can also be used.

Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. Even more preferred are titanium compounds, zirconium compounds and hafnium compounds crosslinked with alkylene or silylene groups.

<Component (B)> The component (B) is an organoaluminum compound. Specific preferred examples of the organoaluminum compound include those represented by the general formula R ₃ Al (wherein R is hydrogen, halogen, siloxy group,
An alkylene bridged siloxy group having 1 to 6 carbon atoms or a hydrocarbon residue having 1 to 10 carbon atoms (preferably 1 to 4), and a plurality of R may be the same or different, provided that 3
Of the Rs present, at least one has 1 to 1 carbon atoms.
0, preferably 1 to 4 hydrocarbon residues).

Specific examples of preferable compounds include (a)
Trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tri n-butyl aluminum, tri n-propyl aluminum, triisoprenyl aluminum, etc., (b) alkyl aluminum Halides such as dimethyl aluminum chloride, diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum dichloride, etc.
Alkyl aluminum hydride, such as dimethyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, etc.
(D) Alkyl aluminum siloxide, for example, dimethyl aluminum (trimethyl siloxide), diethyl aluminum (trimethyl siloxide), etc. can be illustrated. It is also possible to use a mixture of a plurality of these in each group or between each group.

Among these organoaluminum compounds, preferred are trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diisobutylaluminum monochloride, diisobutylaluminum hydride and the like methyl aluminum, derivatives of ethyl aluminum and isobutyl aluminum, That is, in the above formula at least one of R is methyl, ethyl or isobutyl. Even more preferred are trimethylaluminium, triethylaluminum, triisobutylaluminum, and mixtures thereof.

<Component (C)> The component (C) is 0.1 to 9
A fine particle composition comprising 9.9 wt% boric acid. The preferred boric acid content is 1 to 50% by weight, particularly preferably 3 to 35% by weight.

Component (C) is a fine particle composition. Therefore, components other than boric acid (hereinafter sometimes referred to as component (i)) constituting the fine particle composition, that is, 99.9 to 0.1% by weight of the fine particle composition, preferably 99.
The component (component (ii)) accounting for ˜50% by weight, particularly preferably 97-65% by weight, is a particulate material.

In the fine particle composition of component (C), the constituent particles should have a sufficiently small particle size. The preferred particle size is generally 1 to 3000 μm, preferably 5
To 2000 μm, more preferably 10 to 1000 μm
m. In other words, this fine particle composition has a mesh size of 1000 μ
It can be said that the particles have a particle size that substantially passes through the m sieve and does not substantially pass through the 10 μm sieve.

As is typical, component (C) is a fine particle composition comprising boric acid. Where "comprises"
This means that it includes the products of all methods (details described later) of combining both components (components (i) and (ii)) to prepare this fine particle composition, and specifically, boric acid. When (component (i)) and the particulate material (component (ii)) are simply mixed and one component, particularly component (i) (boric acid), is mixed with component (ii) in the form of a solution. It includes a state in which the solvent used is distilled off, and other states. In any case, boric acid itself should also have the above-mentioned particulate properties, especially when boric acid is mixed with the particulate material of component (ii).

(1) Component (i) Component (i) is boric acid. “Boric acid” as the component (i) typically means “oxygen acid formed by hydration of diboron trioxide”. Therefore, in addition to orthoboric acid, which is often simply referred to as boric acid, metaboric acid, tetraboric acid and the like are also included. These can be used alone or as a mixture.

The preferred boric acid for use in the present invention is
It is shown by the following formula. B (O) _n (OH) _m−n [VI] [where n and m are 0 <m−n ≦ 3, 0 ≦ n <
1.5 and n <m ≦ 3, when n = 0, m = 3
When 0 <n <1, 2 <m <3, and when n = 1, m =
2 indicates the number of 1.5 <m <2 when 1 <n <1.5. ] Of these, orthoboric acid (n = 0, m =
3) and metaboric acid (n = 1, m = 2) are particularly preferred.

(2) Component (ii) Component (ii) is a particulate material other than boric acid as the component (i). The particulate material may be organic or inorganic.

As the organic compound, (a) α-olefin polymer, preferably polyethylene, polypropylene,
Polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer and propylene-divinyl Selected from benzene copolymers, (b) aromatic unsaturated hydrocarbon polymers, preferably polystyrene, styrene-
Those selected from divinylbenzene copolymer, styrene-butadiene copolymer and styrene-isoprene copolymer, (c) polar group-containing polymer, preferably polyacrylic ester, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene Examples thereof include those selected from ether, polyethylene terephthalate and polycarbonate, and those known as ion exchange resins.

As the inorganic compound, (d) an inorganic oxide,
Preferably SiO ₂ , Al ₂ O ₃ , AlPO ₄ , Mg
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO,
_{BaO, ThO, SiO 2 -MgO,} SiO 2 -Al 2
_{O 3, SiO 2 -TiO 2,} SiO 2 -V 2 O 5, Si
Those selected from O ₂ —Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO, (e) inorganic halides, preferably those selected from MgCl ₂ , AlCl ₃ and MnCl ₂ , (f) inorganic carbonates, Sulfates or nitrates, preferably Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgC
One selected from O ₃ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ and Mg (NO ₃ ) ₂ , (g) an inorganic hydroxide, preferably Mg (OH) ₂ , Al (OH) _3. And those selected from Ca (OH) ₂ and the like. These can be used in combination within each group and between each group.

(3) Preparation of Component (C) Component (C) can be obtained by contacting a predetermined amount of both component (i) and component (ii) at once or multiple times.

As a method for bringing them into contact with each other, (a) components (i) and (ii) are brought into contact with each other in a solid state and then pulverized, or (b) either component (i) or (ii) is used. After contacting in a solvent capable of dissolving or suspending, a method of removing the solvent, (c) dissolving or suspending both of the components (i) and (ii) in a solvent capable of dissolving or suspending both After
Examples thereof include a method of obtaining a solid component by removing a solvent or coprecipitating a solid. Among them, the method (b) is preferable, and a solvent in which the component (i) is soluble is particularly preferable. Among these methods, the components (i) and (ii) are brought into contact with each other. As the solvent used at this time, water, active hydrogen-containing compounds such as methanol and ethanol, ethers,
Examples thereof include electron-donating compounds such as esters and amines, hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, cyclooctane, and decalin.

The contact mixture obtained by the above operation is
It can be used as the component (C) of the olefin polymerization catalyst of the present invention as it is or after being subjected to an appropriate post-treatment. As a preferred post-treatment, the contact mixture for a predetermined time, a predetermined temperature (usually 0 ~ 600 ℃, preferably 10 ~ 300 ℃, more preferably 10 ~ 200 ℃,
The range) can be used.

<Optional Component> The olefin polymerization catalyst according to the present invention also includes a catalyst containing a purposeful component other than the above-mentioned component (A), component (B) and component (C), That is, as described above, any component can be used as long as the effect is not impaired.

As an optional ingredient that can be added,
(A) active hydrogen-containing compound, preferably water, methanol, ethanol, etc., (b) electron-donating compound, preferably ethers, esters, amines, etc., (c) alkoxy-containing compound, preferably , For example, phenoxy borate, dimethylmethoxyaluminum, phosphite phosphite, tetraethoxysilane, diphenyldimethoxysilane, etc., (d) organoboron compounds, preferably triethylborane, triphenylborane, tris (pentafluorophenyl) borane, Triphenylcarbyl tetrakis (pentafluorophenyl)
Borane etc. can be illustrated.

<Preparation of Catalyst> The olefin polymerization catalyst according to the present invention can be obtained by contacting the component (A), the component (B) and the component (C), and an optional component. The order of contact and the aspect thereof are arbitrary as long as they do not violate the object of the present invention, and each component is added in the polymerization tank or outside the polymerization tank in the presence or absence of a solvent, simultaneously or stepwise. Can be contacted.

The amount of each component used is 1: 0.1 in terms of the atomic ratio of the transition metal (M) in the component (A) to the Al in the component (B).
1: 100000, preferably 1: 3 to 1: 3,000
It is used in the range of 0. The amount of the compound of the component (A) used relative to 1 gram of the component (C) is 1 × 10 ⁻⁵ to 1 gram, preferably 1 × 10 ^{−4 to} 1.0 × 10 ⁻¹ gram, and more preferably 5 × 10. ^{-4 to} 5 x 10 ^-2 grams. The amount of the component (B) used is 1 × 10 ⁻⁴ to 10 grams, preferably 1 × 10 ^{−3 to} 5 per 1 gram of the component (C).
Gram, more preferably 5 × 10 ⁻³ to 2 grams.

Such an olefin polymerization catalyst according to the present invention can be used, if necessary, after being subjected to a prepolymerization which comprises contacting it with an olefin to polymerize a small amount of the olefin. . 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 for controlling the molecular weight, and an inert gas such as nitrogen can be used together for controlling the reaction. Prepolymerization is -78 ° C to 1
It is carried out in the range of 00 ° C, preferably -78 ° C to 50 ° C.
The prepolymerization time is 1 minute to 24 hours, preferably 5 minutes to 1
The prepolymerization amount is 0.01 to 500 g, preferably 0.05.
The range is from about 100 grams, more preferably from 0.1 to 30 grams. The prepolymerization can be carried out at temperature and / or
It is usual to carry out under conditions milder than the main polymerization in terms of pressure.

[Use of Catalyst / Polymerization of Olefin] Needless to say, the catalyst for olefin polymerization according to the present invention is applied to solvent polymerization using a solvent, but liquid phase solvent-free polymerization using substantially no solvent, It is also applied to gas phase polymerization and melt polymerization. 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 350 ° C, preferably -20 to 250 ° C, more preferably 0 to 100 ° C.
° C. The olefin pressure of the reaction system is not particularly limited, but is preferably atmospheric pressure to 3000 kg / cm ² -G, more preferably atmospheric pressure to 1000 kg / cm ² -G, and particularly preferably atmospheric pressure to 50 kg / cm ² -G. , Is the range.
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, other monomers copolymerizable with the above-mentioned α-olefin, such as butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene,
Conjugated and non-conjugated dienes such as 1,8-nonadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like, or cyclopropene, cyclobutene, cyclopentene, norbornene, dicyclopentadiene and the like. It is also effective for copolymerization of cyclic olefins.

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.

Preferred specific examples of the organoaluminum compound include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like.
(B) Diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, (c) diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride,
(D) Aluminum alkoxides such as diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide, and diethylaluminum phenoxide, (e)
Examples include alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane, and methylisobutylalumoxane. It is also possible to use a mixture of a plurality of these. Of these, trialkylaluminum and aluminum alkoxide are preferable. Further preferred are organoaluminum compounds having a methyl group, an ethyl group and an isobutyl group.

[0059]

Example <Example 1> (1) Preparation of catalyst component (C) Silica gel (Davison Co. # 948) 20 was placed in a flask.
Gram and boric acid [B (OH) ₃ ] (Wako reagent special grade)
5 grams was taken and 80 milliliters of water was added.
This was heated to 80 ° C. in an oil bath and held for 10 minutes. After that, set the temperature of the oil bath to 100 ° C,
Most of the water was removed by keeping it for 3 hours while flowing nitrogen. Furthermore, raise the temperature of the oil bath to 150 ° C, and
After holding for a period of time, the component (C) was obtained. (2) Polymerization The 1-liter autoclave was replaced with ethylene, 500 ml of toluene was added, and 30 ml of 1-hexene was added. Then, triisobutylaluminum (TIB
1.0 ml of the pentane solution of A) (145 mg / ml of Tosoh Akzo) was added. Here, 1 ml of the toluene slurry (0.03 g / ml) of the catalyst component (C) obtained above was added, and further, a toluene solution of dimethylsilylene-bis- (tetrahydroindenyl) zirconium dichloride (0.25 1.0 milliliter) was added. 50 ml of hydrogen was added, and polymerization was carried out at 70 ° C. for 45 minutes at an ethylene pressure of 7 kg-G to give 39.5.
Grams of polymer were obtained (ZrY 790000).

<Example 2> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Polymerization The 1 liter autoclave was replaced with ethylene, 500 ml of toluene was added, and 1.2 ml of a pentane solution of triisobutylaluminum (145 mg / ml of Tosoh Akzo Co.) was added.
Here, 5 ml of a toluene slurry (0.03 g / ml) of the catalyst component (C) obtained above was added, and further, a toluene solution of dimethylsilylene-bis- (tetrahydroindenyl) zirconium dichloride (1.0 mg). / Ml) 2.5 ml was added. 50 ml of hydrogen was added, and polymerization was carried out at 70 ° C. for 1.5 hours at an ethylene pressure of 7 Kg-G.
Grams of polymer were obtained (ZrY 117900).

<Example 3> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Polymerization In the polymerization of Example 2, polymerization was carried out under the same conditions as in Example 1 except that after adding 500 ml of toluene, 30 ml of 1-hexene was added, 191 g of a polymer was obtained (ZrY 191000). ).

<Example 4> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Polymerization The 1-liter autoclave was replaced with propylene, 500 ml of toluene was added, and 2.4 ml of a pentane solution of triisobutylaluminum (145 mg / ml of Tosoh Akzo Co.) was added. Here, 10 ml of the toluene slurry (0.03 g / ml) of the catalyst component (C) obtained above was added, and further dimethylsilylene-bis-
4. Toluene solution of (tetrahydroindenyl) zirconium dichloride (1.0 mg / ml) 5.
0 ml was added. Propylene pressure 7 Kg-G,
Polymerization was carried out at 70 ° C. for 1.5 hours to obtain 106 g of a polymer (ZrY 106000).

<Example 5> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Pre-contact of catalyst components In a 100 ml Erlenmeyer flask under a nitrogen atmosphere,
The catalyst component (C) was 1.0 gram. To this, 25 ml of pentane was added, and a pentane solution of triethylaluminum (TEA) (Tosoh Akzo Co., Ltd.) was added.
71 mg / ml) and 4.86 ml, and 1.0 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (3.0 mg / ml) were added. (3) Polymerization The 1-liter autoclave was replaced with ethylene, 500 ml of toluene was added, and 1.0 ml of a pentane solution of triisobutylaluminum (145 mg / ml of Toso Akzo Co., Ltd.) was added.
Here, 5 ml of the catalyst slurry obtained in the above ((2) of Example 5) was added, and 50 ml of hydrogen was added. Polymerization was carried out at 70 ° C. for 1.5 hours at an ethylene pressure of 7 Kg-G to obtain 38.4 g of a polymer (ZrY
38400).

<Examples 6 to 9> (1) Preparation of catalyst component (C) In the preparation of (1) catalyst component (C) of Example 1, the amount of boric acid [B (OH) ₃ ] used is shown. A component (C) was obtained in the same manner except that the amount ratio shown in -1 was used. (2) Polymerization (2) Polymerization of Example 2 as long as it is ethylene polymerization except that the component (A), the component (B), the component (C), the monomer, the comonomer, and the polymerization time shown in Table 1 are used. Then, in the case of ethylene-hexene copolymerization, the polymerization was carried out under the same conditions as the polymerization (2) of Example 3. The results are as shown in Table-1.

<Example 10> (1) Preparation of catalyst component (C) In the preparation of (1) catalyst component (C) of Example 1, 20 g of silica gel (Davison Corporation # 948) was used instead of alumina ( Component (C) was obtained in the same manner except that 20 grams of Akzo grade H) was used. (2) Polymerization In (2) polymerization of Example 2, the same procedure was performed except that the component (C) obtained in the preparation of (1) catalyst component (C) of Example 10 was used as the component (C). The results are as shown in Table-1.

<Examples 11 to 12> (1) Preparation of catalyst component (C) In the preparation of (1) catalyst component (C) of Example 1, instead of using 20 g of silica gel (Davison Corporation # 948), Component (C) was obtained in the same manner except that 20 g of aluminum phosphate (Davison) was used. (2) Polymerization In the polymerization (2) of Example 3 and the polymerization (2) of Example 4, except that the component obtained in the preparation of the catalyst component (1) of Examples 11 to 12 is used as the component (C). I went the same way. The results are as shown in Table-1.

<Example 13> (1) Preparation of catalyst component (C) In the preparation of (1) catalyst component (C) of Example 1, instead of using boric acid [B (OH) ₃ ], metaboric acid was used. [B
Component (C) was obtained in the same manner except that (O) ₁ (OH) ₁ ] (Wako reagent) was used. (2) Polymerization In (2) polymerization of Example 2, the same procedure was carried out except that the component (C) obtained in (1) of Example 13 was used. The results are as shown in Table-1.

Comparative Example 1 (1) Treatment of Silica Gel In the same manner as in (1) of Example 1, except that boric acid [B (OH) ₃ ] was not used, only silica gel was treated. (2) Polymerization In (2) polymerization of Example 2, the same procedure was carried out except that the silica gel treated by the operation of (1) of Comparative Example 1 was used instead of the component (C). The results are as shown in Table-1.

Comparative Example 2 (1) Treatment of Alumina In the case of (1) of Example 10, boric acid [B (OH) ₃ ].
The same procedure was carried out with the exception of not using, and only alumina was treated. (2) Polymerization In (2) polymerization of Example 2, the same procedure was carried out except that the component (C) was replaced with the alumina treated by the operation of (1) of Comparative Example 2. The results are as shown in Table-1.

Comparative Example 3 (1) Treatment of Aluminum Phosphate In (1) of Example 11, boric acid [B (OH) ₃ ].
In the same manner as above, except that no aluminum was used, only aluminum phosphate was treated. (2) Polymerization In (2) polymerization of Example 2, the same procedure was performed except that the aluminum phosphate treated by the operation of (1) of Comparative Example 3 was used instead of the component (C). The results are as shown in Table-1.

<Example 14> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Preparation of Supported Catalyst 2.5 g of the component (C) obtained in (1) of Example 1 was placed in a flask sufficiently replaced with nitrogen, and 50 ml of toluene was added. To this, 10.5 ml of a pentane solution of triisobutylaluminum (145 mg / ml of Tosoh Akzo) was added and stirred for 10 minutes. Further, with stirring, a solution of dimethylsilylene-bis- (tetrahydroindenyl) zirconium dichloride in toluene (10 mg / ml)
3.75 ml was added dropwise. Then, it was dried at room temperature under a nitrogen stream to prepare a supported catalyst. (3) Polymerization The 1-liter autoclave was replaced with ethylene, 500 ml of toluene was added, and 1.2 ml of a pentane solution of triisobutylaluminum (145 mg / ml of Tosoh Akzo) was added.
Here, 0.21 g of the supported catalyst obtained in (2) of Example 14 above was added. 50 ml of hydrogen was added, and polymerization was carried out at 70 ° C. for 2 hours at an ethylene pressure of 7 Kg-G to obtain 12.7 g of a polymer (ZrY 254).
00).

<Example 15> (1) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (2) Preparation of Supported Catalyst 2.5 g of the component (C) obtained in (1) of Example 1 was placed in a flask sufficiently replaced with nitrogen, and 50 ml of toluene was added. A solution of dimethylsilylene-bis- (tetrahydroindenyl) zirconium in toluene (10 mg / milliliter) 3.7 with stirring.
5 ml was dropped and then dried at room temperature under a nitrogen stream to prepare a supported catalyst. (3) Polymerization In the polymerization (3) of Example 14, the same procedure was performed except that 0.17 g of the supported catalyst obtained in (2) of Example 15 was used as the supported catalyst, to obtain 18.9 g of a polymer. (ZrY 37000).

Comparative Example 4 (1) Treatment of Silica Gel The procedure of (1) of Comparative Example 1 was repeated. (2) Preparation of supported catalyst The procedure of (2) Preparation of supported catalyst of Example 14 was repeated except that the silica gel obtained in (1) of Comparative Example 1 was used instead of the component (C). Was prepared. (3) Polymerization In the same manner as in (3) Polymerization of Example 14, 2.0 g of a polymer was obtained, except that 0.21 g of the supported catalyst obtained in (3) of Comparative Example 4 was used as the supported catalyst. (ZrY 4000).

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3] <Example 16> (1) Synthesis of catalyst component (A) Synthesis of dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride According to the method described in Hoechst EP 0545304A1. A) Synthesis of benzoindanone Aluminum chloride 36.4 in a reaction vessel replaced with argon.
g (273 mmol) was weighed, and naphthalene 13.9 g (1
09 mmol), 25 g of α-bromoisobutyl bromide (10
264 ml of a methylene chloride solution (9 mmol) was slowly added dropwise at room temperature. The mixture was stirred overnight and then poured into ice water the next day. 250 ml of methylene chloride were added, concentrated hydrochloric acid was added and the organic phase was separated from the aqueous phase. Since it became an emulsion, it was filtered through Celite, the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was removed under reduced pressure. 25.0 crude product
1 g is obtained (isomer ratio 92: 8). It was purified by column chromatography (Merck, solvent toluene). 12.36 g (58) of the major product (benzoindanone)
%), 1.0554 g (5%) of the minor product was obtained. B) Synthesis of benzoindanol 12.36 g (63 mmol) of benzoindanone was added to THF3.
It was dissolved in 00 ml and 150 ml of methanol, and 3.6 g (95 mmol) of sodium borohydride was added at room temperature. 6
After stirring for an hour, the reaction was stopped with dilute hydrochloric acid, hexane 100 ml
The liquid was separated with x2 and 100 ml x2 of ether. Two stereoisomers of benzoindanol were obtained. Used in the next reaction without purification. C) Synthesis of benzoindene The crude product of benzoindanol was dissolved in 200 ml of toluene and 1.2 g (6.3 mmo) of p-toluenesulfonic acid was dissolved.
l) is added and stirred at 80 ° C. for 15 minutes. The reaction was stopped with a saturated aqueous sodium hydrogen carbonate solution. Separated with toluene, saturated aqueous sodium hydrogen carbonate solution,
Wash with saturated aqueous sodium chloride solution, dry over magnesium sulfate and remove the solvent under reduced pressure. 12.6 g of crude benzoindene product was obtained. It was purified by column chromatography (Merck, solvent hexane-ethyl acetate 0-1%). The yield was 9.66 g (85%). D) Bis (2-methyl-4,5-benzoindenyl)
Synthesis of dimethylsilane 0.41 g of benzoindene in a reaction vessel replaced with argon.
(2.3 mmol) was weighed, toluene 6.2 ml, THF
It was dissolved in 0.3 ml. N-Butyllithium at room temperature 1.
4 ml (equivalent to 2.3 mmol of 1.65 M hexane solution) was added, and the mixture was further stirred at 80 ° C. for 1 hour. Next, 0.14 ml (corresponding to 1.14 mmol) of dichlorodimethylsilane was added at 0 ° C., and the mixture was further stirred at 80 ° C. for 1 hour. The reaction was quenched with water, extracted with ether, the organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure to give a crude product of bis (2-methyl-4,5-benzoindenyl) dimethylsilane. It was purified by silica gel column chromatography (Merck, solvent hexane-methylene chloride 15%). 0.18
65 g (39%). Then it was recrystallized from ether. 0.
0496 g (10%). E) rac-Dimethylsilylene bis (2-methyl-
Synthesis of 4,5-benzoindenyl) zirconium dichloride 0.92 g of bis (2-methyl-4,5-benzoindenyl) dimethylsilane obtained by the above method was added to 25 ml of TH
After being dissolved in F and cooled to -78 ° C, it was diluted with hexane (1.
7M) n-butyllithium was added dropwise in an amount of 3.0 ml,
The temperature was raised over 3 hours. After heating, the mixture was distilled off under reduced pressure, 100 ml of dichloromethane was added, and the mixture was cooled to -78 ° C.
Then, 0.51 mg of zirconium tetrachloride was slowly added, and the temperature was raised to room temperature over 5 hours, and the reaction was carried out at room temperature overnight. After completion of the reaction, solids were separated by filtration, and the supernatant was dried under reduced pressure and washed with 20 ml of toluene three times. After washing
As a result of adding 30 ml of dichloromethane and dissolving and recrystallizing, 0.21 g of orange solid was obtained. ¹ H-NMR showed that the product was rac-dimethylsilylene bis (2-methyl-
It was confirmed to be 4,5-benzoindenyl) zirconium dichloride.

¹ H-NMR (300 MHz CDC
l ₃ ) δ1.36 ppm (s, 6H) δ2.37 pp
m (s, 6H) δ 7.27 to 7.97 ppm (m, 1
2H) (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 3 ml was added. Then, the gas phase part of the autoclave was replaced with ethylene, 60 ml of hydrogen was added, and the polymerization was carried out at an ethylene pressure of 8 kg-G and 90 ° C. for 8 minutes to obtain 26.4.
g of polymer was obtained (ZrY 97800).

Example 17 (1) Synthesis of catalyst component (A) Synthesis of dimethylsilylenebis {4- (1-phenyl-3-methylindenyl)} zirconium dichloride a) Ethyl = α-ethoxycarbonyl-o -Bromocinnamate Synthesis 2-Bromobenzaldehyde 74.5g (402.6mm
ol) was dissolved in 200 ml of benzene, and 53.2 g (402.6 mmol) of dimethyl malonate was added. To this solution, 2.6 ml of piperidine was added, dehydrated by adding Dean Stark, and heated under reflux for 10 hours while removing water. After removing benzene under reduced pressure, the residue was purified by distillation. Ethyl = α-ethoxycarbonyl-o-bromocinnamate 109.1 g
(91%) was obtained. B) Synthesis of ethyl = 3- (2-bromophenyl) -2-ethoxycarbonyl-3-methylpropionate Ethyl = α-ethoxycarbonyl-o-bromocinnamate 50.98 g (170.5 mmol) and copper bromide 1.0 g
Was dissolved in 500 ml of ether, and 56.7 ml of an ether solvent of methyl magnesium bromide (17
5.6 mmol) was added dropwise. The mixture was stirred overnight at room temperature, an aqueous solution of ammonium chloride was added thereto, the layers were separated, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give ethyl 3- (2-bromophenyl) -2 -Ethoxycarbonyl-3-methylpropionate was obtained. C) Synthesis of ethyl = 3- (2-bromophenyl) -3-methylpropionate Unpurified ethyl = 3- (2-bromophenyl) -2-ethoxycarbonyl-3-methylpropionate 52.9
6 g (168.13 mmol) of dimethyl sulfoxide 25
It was dissolved in 0 ml and 3 ml of water, 14 g of lithium chloride was added thereto, and the mixture was heated at 150 ° C. for 2.5 hours. After cooling, dimethyl sulfoxide was removed under reduced pressure, an aqueous sodium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of ammonium chloride, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Further, if the concentrated residue is subjected to residual purification, ethyl = 3- (2-bromophenyl) -3-
28.04 g (65%) of methyl propionate was obtained. D) Synthesis of 3- (2-bromophenyl) -3-methylpropionic acid 28.04 g (109.1 mmol) of ethyl = 3- (2-bromophenyl) -3-methylpropionate in 200 ml of ethanol and 100 ml of water After dissolution, 12.2 g (218.2 mmol) of potassium hydroxide was added. Add this solution to 5
Heated to reflux for hours. After leaving it as it was at room temperature, about half of the solvent was removed and diluted hydrochloric acid was added. Dichloromethane was added to this, and an aqueous solution of ammonium chloride was added thereto. The organic layer was separated, dried over magnesium sulfate, and then evaporated under reduced pressure to remove 3- (2-bromophenyl) -3-methylpropione. 27.97 g (quant.) Of acid was obtained. E) Synthesis of 4-bromo-3-methyl-1-indanone 3- (2-bromophenyl) -3-methylpropionic acid 10.36 g (42.63 mmol) in thionyl chloride 30 m
1 was added and the mixture was heated under reflux for 1.5 hours. Next, excess thionyl chloride was removed, and a small amount of carbon tetrachloride was added to remove it. The obtained crude product of acid chloride is dissolved in carbon tetrachloride,
A suspension of 7.4 g (55.42 mmol) of aluminum chloride in 60 ml of carbon tetrachloride was added dropwise at 0 ° C. This solution at 0 ℃
After stirring for 30 minutes at room temperature and overnight at room temperature, concentrated hydrochloric acid and dichloromethane were added, the layers were separated, the organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Further purification by silica gel column chromatography gave 7.71 g (80%) of 4-bromo-3-methyl-1-indanone. F) Synthesis of dimethylbis {4- (3-methyl-1-oxoindanyl)} silane 4-bromo-3-methyl-1-indanone 6.918 g
Paratoluenesulfonic acid 175m to (30.75mmol)
g (3 mmol), ethyl orthoformate 7.6 ml (46.1)
2 mmol), 17.1 ml of ethylene glycol (307.
(5 mmol) was added and the mixture was stirred at room temperature overnight. An aqueous solution of sodium hydrogencarbonate was added thereto, extracted with ether, and further washed several times with an aqueous solution of sodium hydrogencarbonate. The ether layer was separated, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. 8.374 g of crude ketal in this way
(Quant.) Was obtained. This was dissolved in 100 ml of ether, and 20.4 ml (32.69 mmol) of a hexane solution of normal butyl lithium was added dropwise at -5 ° C. This-
The mixture was stirred at 5 ° C. for 2.5 hours, and dimethyldichlorosilane 1.
89 ml (15.6 mmol) was added, and the mixture was further subjected to 0 ° C. for 1 hour, room temperature for 2 hours, and reflux for 1 hour, and then left overnight. After adding an ammonium chloride aqueous solution thereto, the organic layer was separated, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. Acetone and p-toluenesulfonic acid were added to the obtained concentrated residue, and the mixture was stirred at room temperature for 2.5 hours. An aqueous solution of sodium hydrogen carbonate was added thereto, and the layers were separated. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The concentrated residue was purified by silica gel chromatography to obtain 4.05 g (75%) of dimethylbis {4- (3-methyl-1-oxoindanyl)} silane. G) Synthesis of dimethylbis {4- (1-phenyl-3-methylindenyl)} silane Dimethylbis {4- (3-methyl-1-oxoindanyl)} silane 1.54 g (4.425 mmol) with 90 ml of ether Dissolve in 9 ml of tetrahydrofuran, and add phenylmagnesium bromide ether solution at 0 ° C to 7.8 m.
1 (13.28 mmol) was added. This was stirred at room temperature overnight and heated to reflux for a further 2 hours. After that, an aqueous solution of ammonium chloride was added, and the layers were separated. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Furthermore, 70 ml of toluene and 45 ml of paratoluenesulfonic acid (5 mm
ol) was added and the mixture was stirred at 70 ° C. for 20 minutes. An aqueous solution of sodium hydrogen carbonate was added thereto, and the layers were separated. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. This was purified by silica gel column chromatography to obtain 998 mg (48%) of dimethylbis {4- (1-phenyl-3-methylindenyl)} silane. H) dimethylsilylene bis {4- (1-phenyl-3
Synthesis of -Methylindenyl)} zirconium dichloride The following operations were all carried out under a nitrogen atmosphere, and the solvent used was one that had been thoroughly dehydrated and deoxygenated.

A solution of 0.67 g (1.43 mmol) of dimethylbis {4- (1-phenyl-3-methylindenyl)} silane synthesized as described above in 30 ml of toluene was added at 0 ° C. with normal butyl lithium-hexane. Solution 1.
74 ml (2.85 mmol) was slowly added dropwise. 0 ° C
After stirring for 15 minutes at room temperature, the mixture was stirred at room temperature for 4 hours and at 45 ° C. for 2 hours. After evaporating the solvent of the reaction solution, the obtained red solid was dissolved in 30 ml of diethyl ether. The solution was cooled to −78 ° C. and zirconium tetrachloride / diethyl ether complex was slowly added. After stirring at −78 ° C. for 1 hour, the temperature was gradually raised to room temperature over 2 hours while stirring, and the mixture was further stirred at room temperature for 15 hours. Then, the solvent of the reaction solution was distilled off, and 40 m of methylene chloride was added to the obtained solid.
1 was added, the soluble part was extracted, and the solvent was distilled off. Recrystallization from methylene chloride / hexane gave a dark purple solid of dimethylsilylenebis {4- (1-phenyl-3-methylindenyl)} zirconium dichloride (yield 55%). (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 3 ml was added. Then, the gas phase part of the autoclave was replaced with ethylene, 60 ml of hydrogen was added, and polymerization was carried out at an ethylene pressure of 8 kg-G and 90 ° C. for 40 minutes, and 15.
0 g of polymer was obtained (ZrY 55600).

Example 18 (1) Synthesis of catalyst component (A) Synthesis of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride a) Dimethylbis {1- (2-methyl-4- Synthesis of (phenyl-1,4-dihydroazurenyl)} silane 2.22 g (15.66 mmol) of 2-methylazulene was dissolved in 30 ml of hexane, and 15.6 ml (15.66 mmol) of cyclophenyl ether solution of phenyllithium.
Was added in small portions at 0 ° C. The solution was stirred at room temperature for 1 hour. This is cooled to -78 ° C and tetrahydrofuran 30 is added.
ml was added. Dimethyldichlorosilane 0.95
ml (7.83 mmol) was added and the temperature was raised to room temperature. Furthermore, it heated at 50-60 degreeC for 1.5 hours. An aqueous solution of ammonium chloride was added to this, and the layers were separated. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained crude product was purified by silica gel chromatography to obtain dimethylbis {1- (2-methyl-4-phenyl-1,4-
1.48 g (38%) of dihydroazurenyl)} silane were obtained. (B) Synthesis of dimethylsilylene bis (2-methyl-4-phenylazulenyl) zirconium dichloride The following operations were all carried out under a nitrogen atmosphere, and the solvent used was one that had been sufficiently dehydrated and deoxygenated.

0.768 g (1.55 mmol) of dimethylbis {1- (2-methyl-4-phenyl-1,4-dihydroazurenyl)} silane synthesized as described above was dissolved in 15 ml of diethyl ether, 1.98 ml of a hexane solution of normal butyl lithium was added dropwise at -76 ° C, the temperature was gradually raised, and the reaction was carried out at room temperature for 12 hours. Subsequently, the solvent was distilled off under reduced pressure, the residue was washed with hexane and then the solvent was distilled off again, 20 ml of a mixed solvent of toluene / diethyl ether = 40/1 was added, and 0.325 g of zirconium tetrachloride (-1. 40 mmol) was added. Then, the temperature was gradually raised and the reaction was carried out at room temperature for 15 hours. After the reaction was completed, the mixture was filtered, the remaining solid was extracted with toluene, and the filtrate was concentrated.
Hexane was added, and reprecipitation and recrystallization were performed to obtain a racemic body of dimethylsilylenebis (2-methyl-4-phenylazulenyl) zirconium dichloride as a brownish yellow solid. (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 3 ml was added. After that, the gas phase part of the autoclave was replaced with ethylene, 60 ml of hydrogen was added, and polymerization was carried out at 90 ° C. for 20 minutes at an ethylene pressure of 8 kg-G.
9 g of polymer was obtained (ZrY 66300).

<Example 19> (1) Synthesis of catalyst component (A) Synthesis of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride a) 1-phenyl-2,3,4,5- Synthesis of tetramethylphosphole In a nitrogen atmosphere, 13.6 g of aluminum chloride was suspended in 150 ml of dichloromethane. 2-butin 15m here
150 ml of dichloromethane containing 1 was added dropwise in 20 minutes in an ice bath, and the mixture was stirred for 30 minutes as it was. 3 at room temperature
After reacting for 0 minutes, a dark red solution was obtained. This was cooled to −60 ° C., and 150 ml of dichloromethane containing 19.9 g of dichlorophenylphosphine was added dropwise over 20 minutes. The temperature was returned to room temperature with stirring to obtain a dark red solution.

35 ml of tri-n-butylphosphine dissolved in 150 ml of dichloromethane was added dropwise thereto at -30 ° C over 10 minutes. The solution became pale yellow. The solvent was removed under reduced pressure to obtain a yellowish brown viscous solid.

It was extracted with 700 ml of hexane, and the extract was washed with 200 ml of an aqueous sodium hydrogen carbonate solution (5 wt%) and 400 ml of pure water. 30 g of anhydrous magnesium sulfate was added as a drying agent, and the mixture was left standing overnight.

The anhydrous magnesium sulfate was filtered to remove the hexane solution. Pale yellow oily 1-phenyl-2,3,3
4,5-Tetramethylphosphole was obtained with a yield of 80%. B) Synthesis of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride Dry 2.89 g (13.4 mmol) of 1-phenyl-2,3,4,5-tetramethylphosphole in an argon atmosphere. It was dissolved in 50 ml of tetrahydrofuran. 0.37 g of particulate metallic lithium was added thereto at room temperature, and the solution gradually changed to deep red. The reaction was stirred for 3 hours.

After the reaction, the dark red solution portion was separated from the lithium reaction residue, and 0.60 g of anhydrous aluminum chloride (4.
(50 mmol) was added over 10 minutes, and the mixture was further reacted for 3 hours. This is designated as solution A.

In a nitrogen gas atmosphere, 1.48 g (6.35 mmol) of zirconium tetrachloride was suspended in 15 ml of toluene and placed in an ice bath. The above-mentioned liquid A was dropped into this in 15 minutes,
The reaction was continued for another 30 minutes. After returning to room temperature, the solvent was removed under reduced pressure and the mixture was dried.

The dried solid was dried with diethyl ether 130.
After extraction with ml, removal of the solvent and drying to dryness, followed by the same operation with 60 ml of dry n-heptane, the result was orange bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride 1 .24 g (44%) was obtained. (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 2 ml was added. Then, the gas phase part of the autoclave was replaced with ethylene, 60 ml of hydrogen was added, and polymerization was carried out at an ethylene pressure of 8 kg-G and 90 ° C. for 45 minutes.
2 g of polymer was obtained (ZrY 117800).

Example 20 (1) Synthesis of catalyst component (A) Dimethylsilylene bis {4- (1-indolyl) -2-
Synthesis of methyl indenyl} zirconium dichloride a) Synthesis of diethyl 2- (2-bromobenzyl) -2-methylmalonate Sodium hydroxide 14.0 (34
9 mmol) was weighed and suspended in 200 ml of toluene, and while cooling with an ice bath, 60.0 ml (320 mmol) of ethyl ethyl malonate in 100 ml of a toluene solution.
Was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours, and then 2-bromobenzyl bromide 80.0 g (320
(100 mmol) in toluene solution was added dropwise, and the mixture was stirred as it was overnight. The reaction mixture was poured into diluted hydrochloric acid to stop the reaction, and the organic layer was washed with water, dried and concentrated to give 120
g of yellow oily diethyl 2- (2-bromobenzyl) -2-methylmalonate was obtained. Yield 100%. B) Synthesis of ethyl 3- (2-bromophenyl) -2-methylpropionate 108 g (310 mmol) of diethyl 2- (2-bromobenzyl) -2-methylmalonate was added to dimethyl sulfoxide 3
Dissolved in 50 ml, 26.4 g of lithium chloride (620
mmol) and 5.6 ml of water (310 mmol) were added. 180
After stirring at 8 ° C for 8 hours, the product was extracted with n-hexane and concentrated to obtain 84.1 g of yellow oily ethyl 3- (2-bromophenyl) -2-methylpropionate. Yield 10
0%. C) Synthesis of 3- (2-bromophenyl) -2-methylpropionic acid 65.5 g (243 mmol) of ethyl 3- (2-bromophenyl) -2-methylpropionate and potassium hydroxide 2
0.5 g (364 mmol) was dissolved in 250 ml of ethanol, heated under reflux for 6 hours, and then 500 ml of water was added. After adding 50 ml of concentrated hydrochloric acid, the product was extracted with toluene, dried and concentrated to give 37.8 g of a yellow oily 3- (2
-Bromophenyl) -2-methylpropionic acid was obtained.
Yield 89%. D) Synthesis of 4-bromo-2-methylindan-1-one 3- (2-bromophenyl) -2-methylpropionic acid 52.5 g (215 mmol) to polyphosphoric acid 210 g, o-
250 ml of dichlorobenzene was added, and the mixture was stirred at 140 ° C for 6 hours. 300 ml of water was added, the product was extracted with n-hexane and ether, dried and concentrated, and the residue obtained was distilled to give 27.3 g of colorless crystals of 4-
Bromo-2-methylindan-1-one was obtained. Yield 5
6%. E) Synthesis of 4- (1-indolyl) -2-methylindanone-1-one 4-bromo-2-methylindan-1-one 21.5 g
(95.4 mmol), indole 11.4 g (97.1 mm)
ol), anhydrous potassium carbonate 13.4 g and copper (II) oxide
0.49 g was weighed in a reaction vessel and dissolved in 19 ml of N, N-dimethylformamide. After heating under reflux for 5 days, the reaction mixture was dissolved in ether and water, and the insoluble material was filtered through Celite. The organic layer is separated, washed with water, dried,
Concentrated and purified by column chromatography (Fuji Silysia basic gel, ethyl acetate / n-hexane), 4.23 g of black oily 4- (1-indolyl)-
2-Methylindanone-1-one was obtained. Yield 17%. F) 4- (1-Indolyl) -2-methylindan-
Synthesis of 1-ol 4- (1-indolyl) -2-methylindanone-1-
4.23 g (16.2 mmol) of ON was dissolved in 80 ml of tetrahydrofuran, and sodium borohydride 1.08
g (28.5 mmol) was added, and further methanol 40 m
1 was slowly added and stirred overnight at room temperature. The reaction was stopped with a saturated ammonium chloride aqueous solution, the product was extracted with n-hexane and ether, dried and concentrated, and then purified by column chromatography (Fuji Silysia basic gel, ethyl acetate / n-hexane). 2.74g
An oily mixture of two diastereomers of 4- (1-indolyl) -2-methylindan-1-ol was obtained. Yield 64%. G) Synthesis of 7- (1-indole) -2-methylindene 4- (1-indolyl) -2-methylindan-1-ol 2.74 g (10.4 mmol) was dissolved in 50 ml of toluene and p-toluene was added. 0.24 g of sulfonic acid was added, and the mixture was stirred at 70 ° C. for 1 hour. After quenching the reaction by adding saturated aqueous sodium hydrogen carbonate, extraction with ether, drying, concentration, and purification by column chromatography (Fuji Silysia Company's basic gel, n-hexane), 1.68 g of a yellow solid was obtained. To give 7- (1-indole) -2-methylindene. Yield 66%. H) Synthesis of bis {7- (1-indolyl) -2-methylindenyl} dimethylsilane Under a nitrogen atmosphere, 1.64 g (6.69 mmol) of 7- (1-indole) -2-methylindene was dried in toluene 34
ml and dry tetrahydrofuran 1.7 ml mixed solvent, and n-butyllithium n-hexane solution (1.68M) 4.0 ml (6.7 mmol) was added dropwise at 0 ° C. After heating at 80 ° C. for 30 minutes, 0.36 ml (3.0 mmol) of dichlorodimethylsilane was added at 0 ° C. 80
After stirring at 0 ° C for 2 hours, 50 ml of saturated aqueous sodium hydrogen carbonate was added to stop the reaction, and the product was extracted with ether. After the extract was dried and concentrated, column chromatography (basic gel manufactured by Fuji Silysia Ltd., methylene chloride / n-hexane), followed by column chromatography (silica gel,
Purification with toluene / n-hexane) yielded 0.86 g of a brown oily bis {7- (1-indolyl) -2-methylindenyl} dimethylsilane. Yield 24%. Li) dimethylsilylene bis {4- (1-indolyl)
Synthesis of 2-methyl-indenyl} zirconium dichloride Under nitrogen atmosphere, bis {7- (1-indolyl) -2-methylindenyl} dimethylsilane 0.82 g (1.5 mm
ol) was dissolved in a mixed solvent of 12 ml of dry toluene and 0.6 ml of dry tetrahydrofuran, and 1.8 ml of a hexane solution of n-butyllithium (1.71M) was added thereto at 0 ° C.
(3.1 mmol) was added. After heating under reflux for 4 hours, the solvent was distilled off under reduced pressure to obtain a red solid. To this 9 ml of toluene
And 0.5 ml of ether were added, and 0.35 g (1.5 mmol) of zirconium tetrachloride was added at -45 ° C. After stirring overnight while gradually warming to room temperature, the solvent was distilled off under reduced pressure, dry methylene chloride was added to this, the resulting suspension was filtered, and the precipitate was washed with dry n-hexane. , Dried under reduced pressure to give a yellow solid dimethylsilylene bis {4- (1
0.21 g of -indolyl) -2-methylindenyl} zirconium dichloride was obtained. (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 3 ml was added. After that, the gas phase part of the autoclave was replaced with ethylene, 60 ml of hydrogen was added, and polymerization was carried out at an ethylene pressure of 8 kg-G and 90 ° C. for 50 minutes to obtain 3.7.
g of polymer was obtained (ZrY 20600).

<Example 21> (1) Synthesis of catalyst component (A) The same procedure as (1) Synthesis of catalyst component (A) in Example 16 was carried out. (2) Preparation of catalyst component (C) The same procedure as (1) Preparation of catalyst component (C) in Example 1 was carried out. (3) Polymerization The 1.5 liter autoclave was replaced with nitrogen, 500 ml of toluene was added, and a toluene solution of triisobutylaluminum (manufactured by Tosoh Akzo) (198 g /
2 ml of l) was added. Here, 4 ml of the toluene slurry (30 g / l) of the catalyst component (C) obtained above was added, and further a toluene solution of the catalyst component (A) (1.0 mm
ol / l) 3 ml was added. Then, the gas phase part of the autoclave was replaced with propylene, 90 ml of hydrogen was added, and polymerization was carried out at a propylene pressure of 6 kg-G and 70 ° C. for 60 minutes to obtain 1
3.1 g of polymer was obtained (ZrY 72800).

The polymerization results obtained in Examples 16 to 21 are as shown in Table 2.

[0092]

[Table 4]

[0093]

Industrial Applicability According to the present invention, it is possible to provide a polyolefin having good particle properties in a high yield without using expensive methylalumoxane. As described above in.

Claims (5)

[Claims] 1. A catalyst for olefin polymerization, which comprises the following components (A), (B) and (C). Component (A): Group 4 to 6 transition metal compound of the periodic table having at least one conjugated five-membered ring ligand Component (B): Organoaluminum compound Component (C): 0.1 to 99.9% by weight A fine particle composition comprising boric acid. 2. The component (A) comprises the following general formulas [I] and [I]:
I], [III] or [IV],
The olefin polymerization catalyst according to claim 1. Embedded image [Here, A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Z is a bonding group that bridges at an arbitrary position, Z is a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom bonded to Me, and Q ′ is a conjugated five-membered ring system. Me is a metal atom selected from Groups 4 to 6 of the Periodic Table, and X and Y.
Is a hydrogen group bonded to Me, a halogen group, a hydrocarbon group,
An alkoxy group, an amino group, a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group are shown respectively. ] 3. The component (B) is an organoaluminum compound represented by the following general formula [V], wherein:
The catalyst for olefin polymerization according to 1. R ₃ Al [V] [wherein R is hydrogen, halogen, siloxy group, alkylene bridged siloxy group having 1 to 6 carbon atoms or 1 to 1 carbon atoms]
A hydrocarbon residue of 0 and a plurality of Rs may be the same or different, provided that at least one of three Rs is a hydrocarbon residue having 1 to 10 carbons. ] 4. The component (C) comprises (i) the following general formula [VI]:
Boric acid of 0.1 to 99.9% by weight and (ii)
The following (a), (b), (c), (d), (e),
Fine particle material 99.9 to be selected from (f) and (g)
A fine particle composition comprising 0.1% by weight.
The olefin polymerization catalyst according to any one of 3 above. B (O) _n (OH) _mn [VI] [where n and m are m = 3 when n = 0, 0 <
2 <m <3 when n <1, m = 2 when n = 1, 1
When <n <1.5, the number of 1.5 <m <2 is shown. However, m + n = 3. ] (A) Polyethylene, polypropylene, polybutene
Α selected from 1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer and propylene-divinylbenzene copolymer
-Olefin polymer, (b) polystyrene, styrene-
Aromatic unsaturated hydrocarbon polymer selected from divinylbenzene copolymer, styrene-butadiene copolymer and styrene-isoprene copolymer, (c) polyacrylic ester, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene ether , A polar group-containing polymer selected from polyethylene terephthalate and polycarbonate, (d) SiO ₂ , Al ₂ O ₃ , MgO, Zr.
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO,
_{ThO, SiO 2 -MgO, SiO 2} -Al 2 O 3, S
_{iO 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -C
Inorganic oxide selected from r ₂ O ₃ and SiO ₂ —TiO ₂ —MgO, (e) MgCl ₂ , AlCl ₃ and M
Inorganic halide selected from nCl ₂ , (f) Na ₂
CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al ₂
(SO ₄ ) ₃ , BaSO ₄ , KNO ₃ and Mg (NO
₃ ) ₂ inorganic carbonates, sulfates or nitrates, (g) Mg (OH) ₂ , Al (OH) ₃ and Ca
An inorganic hydroxide selected from (OH) ₂ . 5. 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 4 for polymerization.