JP3441442B2 - Olefin polymerization catalyst component - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a catalyst used for producing a stereoregular polyolefin. Specifically, the present invention provides a catalyst for olefin polymerization comprising a specific metallocene compound, that is, an asymmetric novel transition metal compound having a bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridge structure and alumoxane. Regarding

[0002]

2. Description of the Related Art A so-called Kaminsky catalyst is well known as a homogeneous catalyst for olefin polymerization. This catalyst has a feature that the polymerization activity is very high and a polymer having a narrow molecular weight distribution can be obtained.

Transition metal compounds for producing isotactic polyolefin include ethylene bis(indenyl)zirconium dichloride and ethylene bis(4,5,5).
6,7-Tetrahydroindenyl)zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) is known, but the molecular weight of the produced polyolefin is small, and when it is produced at a low temperature, a high molecular weight product is obtained but the polymerization activity is high. There is a problem such as low.

It has been known that a high molecular weight compound can be produced by using a hafnium compound instead of zirconium (Journal of Molecular Catalysis,
56 (1989) p.237-247), this method has a problem that the polymerization activity is low. Further, dimethylsilylbis-substituted cyclopentadienyl zirconium dichloride and the like are disclosed in JP-A-1-301704, Polymer Preprints, J.
apan vol. 39, No. 6 p. 1614 to 1616 (1990), etc., but there are no reports of catalysts that simultaneously satisfy high polymerization activity and high molecular weight.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention
An object of the present invention is to provide a polymerization method for obtaining a polypropylene polymer having a high molecular weight (number average molecular weight of 70,000 or more) that can be injection-molded in a high yield.

[0006]

[Summary of the Invention] <Summary> The present invention has been made as a result of studies to solve the above problems. That is, the olefin polymerization catalyst component according to the present invention is a transition metal compound represented by the following general formula [I].

[0007]

[Chemical 2] (In the formula, M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and two R are present.
¹ may be the same or different, and have 1 to 6 carbon atoms,
It is a monovalent hydrocarbon residue or a hydrocarbon residue containing silicon, and two R ^{2 s that} may be present may be the same or different. It is a divalent hydrocarbon residue or a hydrocarbon residue containing silicon, which has 4 to 20 carbon atoms, and R ³ has 1 to 30 carbon atoms.
A divalent hydrocarbon residue or a hydrocarbon residue containing silicon or germanium, wherein X and Y are each independently hydrogen or halogen, or a carbon number of 1 to 2.
0 is a monovalent hydrocarbon residue or a hydrocarbon residue containing nitrogen, oxygen or silicon. However, the substituent R ¹
The two five-membered ring ligands with R ² and R ² are asymmetric with respect to the plane containing M in terms of their relative position via the group R ³ . )

<Effect> By using the catalyst component of the present invention, it becomes possible to produce a stereoregular polyolefin having a high molecular weight in a high yield. Originally antagonistic high polymerization activity and high molecular weight were compatible, the characteristics of the catalyst of the present invention,
For example, due to the use of asymmetric metallocene compounds, it is understood that it was unexpected.

DETAILED DESCRIPTION OF THE INVENTION <Catalyst> The present invention relates to the use of a transition metal compound represented by the following general formula [I] as a catalyst component for olefin polymerization.

<Component (A)> (1) One catalyst component (A) used in the present invention is a transition metal compound represented by the following general formula [I].

[Chemical 3] (In the formula, M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and two R are present.
¹ may be the same or different, and have 1 to 6 carbon atoms,
Preferably, it is a monovalent hydrocarbon residue or a hydrocarbon residue containing silicon of 1 to 4, two R ^{2 s} may be the same or different, and the two R 5 A divalent hydrocarbon residue having 4 to 20 carbon atoms, preferably 4 to 8 carbon atoms bonded to adjacent carbon atoms, or a hydrocarbon residue containing silicon, and R ³ has 1 to 30 carbon atoms. A divalent hydrocarbon residue having 2 to 20 carbon atoms, or a hydrocarbon residue containing silicon or germanium, X
And Y are each independently hydrogen or halogen, or 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, 1
A hydrocarbon residue or a hydrocarbon residue containing nitrogen, oxygen or silicon. )

The metallocene compound of the formula [I] used in the present invention has two five-membered ring ligands having the substituents R ¹ and R ² in terms of the relative position via the group R ³ .
The major feature is that it is asymmetric with respect to the plane containing M.

Here, "asymmetric with respect to the plane containing M in terms of relative position via the group R ³ "means

[Chemical 4] It is shown that these two substituted five-membered rings that face each other with respect to each other are not in a mirror image of the substance with respect to the plane containing M.

The asymmetric state in that case is roughly classified into two.
There can be types. That is, one is the case where the positions of the substituents R ¹ and R ² of the both-substituted 5-membered ring ligand are not mirror images of the substance with respect to the plane containing M, X and Y.
In that case, even if R ¹ and R ² are the same between both substituted five-membered ring ligands, both substituted ligands are not in a mirror image relationship with the substance. Another one of the asymmetric, even in relation entity and mirror image with respect to the position of the two substituents ligand substituents R ¹ and R ^2, R ¹ and at least one of R ² is both substituted five-membered ring coordinated This is the case when the children are not the same. In that case,
For example, even if the position of R ¹ has a relationship with the substance and the mirror image, the two substituted 5-membered ring ligands have no relationship with the substance and the mirror image because the types are different. However, the asymmetric state in the present invention means only the former.

As described above, R ¹ has 1 to 6 carbon atoms,
It is a monovalent hydrocarbon residue or a hydrocarbon residue containing silicon. More specifically, R ¹ is a saturated hydrocarbon group such as alkyl or cycloalkyl, an unsaturated hydrocarbon group such as alkenyl, or a silicon-containing hydrocarbon group such as alkylsilyl. Specific examples include methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, t
-Butyl, n-amyl, i-amyl, n-hexyl, cyclopropane, allyl, trimethylsilyl and dimethylethylsilyl groups are exemplified. Of these, preferred are methyl, ethyl, n-propyl, i-propyl, n
An alkyl group such as -butyl, i-butyl, t-butyl and the like.

More specifically, R ² is a saturated hydrocarbon group such as alkylene or cycloalkylene, an unsaturated hydrocarbon group such as alkadienylene or arylene, or a hydrocarbon group containing silicon such as alkylsilylalkylene or alkylsilylalkenylene. is there. Specific examples include butylene, methylbutylene, 2-methylbutylene, 1,2-dimethylbutylene, cyclopropylbutylene, 1,3-butadienylene, methyl-1,3-butadienylene, phenylbutylene, phenyl-1,3-butadienylene. , Trimethylsilyl butylene, trimethylsilyl-1,3-
Examples include butadienylene, dimethylethylsilylbutylene, and dimethylethylsilyl-1,3-butadienylene groups. Of these, preferred are alkylene groups such as butylene and methylbutylene, 1,3-butadienylene,
It is an alkadiennylene group such as methyl-1,3-butadienylene.

More specifically, R ³ is a saturated hydrocarbon residue such as alkylene or cycloalkylene, an unsaturated hydrocarbon residue such as arylene, or a hydrocarbon residue containing silicon or germanium such as alkylsilylene or alkylgermylene. Is. Preferred are alkylene, cycloalkylene, arylene, and alkylsilylene groups.

More specifically, X and Y are each independently hydrogen or halogen (eg, fluorine, chlorine,
Bromine, iodine, preferably chlorine), or carbon number 1-20
Is a monovalent hydrocarbon residue or a hydrocarbon residue containing silicon or germanium (preferably those described above for R ¹ , particularly preferably methyl).

Representative synthetic route of the compound [I] of the present invention
Is as follows. In addition, HR ^aIs

[Chemical 5] Is shown. H_TwoR^a+n-C_FourH₉Li→HR^aLi+n-C_FourH
₉ 2HR^aLi+R^ThreeCl_Two→R^Three(HR^a)_Two+2Li
Cl R^Three(HR^a)_Two+2・n-C_FourH₉Li→R^Three(R^a
Li)_Two+2・n-C _FourH₉ R^Three(R^aLi)_Two+ZrCl_Four→R^Three(R^a)_TwoZr
Cl_Two+2LiCl

The following may be mentioned as non-limiting examples of the above-mentioned transition metal compounds. In addition, although these compounds are simply referred to by their chemical names, it goes without saying that their three-dimensional structure has asymmetry in the present invention. (1) ethylenebis-(2-methylindenyl)zirconium dichloride, (2)1,1,2,2-tetraphenylethylenebis-(2-methylindenyl)zirconium dichloride, (3)dimethylsilylenebis-( 2-
Methylindenyl)zirconium dichloride, (4)diphenylsilylenebis-(2-methylindenyl)zirconium dichloride,(5)dimethylgermylenebis-
(2-methylindenyl)zirconium dichloride,
(6) Ethylenebis-(2-methyltetrahydroindenyl) zirconium dichloride, (7) 1,1,2,2
-Tetraphenylene ethylene bis-(2-methyltetrahydroindenyl) zirconium dichloride, (8) dimethylsilylenebis-(2-methyltetrahydroindenyl) zirconium dichloride, (9) diphenylsilylenebis-(2-methyltetrahydroindenyl) Zirconium dichloride, (10) dimethylgermylene bis-
(2-methyltetrahydroindenyl)zirconium dichloride,

(11) Ethylenebis-(2-ethylindenyl)zirconium dichloride, (12) 1,1,2,2
-Tetraphenylethylene bis-(2-ethylindenyl) zirconium dichloride, (13) dimethylsilylene bis-(2-ethylindenyl) zirconium dichloride, (14) diphenylsilylene bis-(2-ethylindenyl) zirconium dichloride, (15) Ethylenebis-(2-ethyltetrahydroindenyl) zirconium dichloride, (16) Ethylenebis-(2-n-propylindenyl) titanium dichloride, (17) Ethylenebis-(2-methylindenyl) zirconium dimethyl ,
(18) 1,1,2,2-Tetraphenylethylene bis-
(2-methylindenyl)zirconium dimethyl, (1
9) Dimethylsilylene bis-(2-methylindenyl)
Titanium dimethyl, (20) ethylene (2-methylindenyl) (2-ethylindenyl) zirconium dichloride,

(21) ethylene(2-methyltetrahydroindenyl)(2-ethyltetrahydroindenyl)zirconium dichloride, (22) ethylenebis-(2-trimethylsilylindenyl)zirconium dichloride,
(23) Dimethylsilylene bis-(2-cyclopropyltetrahydroindenyl) hafnium dichloride, (24)
Ethylene bis-(2-methyl-4-methylindenyl)
Hafnium dichloride, (25) ethylenebis-(2-methyl-5-methylindenylzirconium dichloride,
(26) dimethylsilylenebis-(2-methylindenyl)zirconium methyl (methylphenylamine),
(27) Dimethylsilylenebis-(2-methylindenyl)zirconium butoxycyclolide, (28)Dimethylsilylenebis-(2-methylindenyl)zirconium bis(trimethylsilyl), (29)Dimethylsilylenebis-(2-methylindene) Examples thereof include (nyl) zirconium trimethylsilyl chloride and (30) dimethylsilylene bis-(2-methylindenyl) zirconium bis(trimethylsilyl) methyl chloride.

<Component (B)> Another component (component (B)) used in the present invention is represented by the following general formula [II]
Alternatively, it is an alumoxane represented by [III].

[0023]

[Chemical 6] (Here, m is a number of 4 to 30, preferably 10 to 25, R ⁴ is a hydrocarbon residue, preferably 1 to 1 carbon atoms.
0, particularly preferably having 1 to 4 carbon atoms. )

The component (B) is a product obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, (a) methyl alumoxane, ethyl alumoxane, propyl alumoxane, butyl alumoxane, isobutyl alumoxane obtained from one type of trialkylaluminum, and (b) two types of trialkylaluminum obtained from water. Examples thereof include methyl ethyl alumoxane, methyl butyl alumoxane and methyl isobutyl alumoxane. Of these, methylalumoxane is particularly preferable.

A plurality of these alumoxanes can be used in combination in each group and between each group, and they can be used in combination with other alkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible to do so.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether, (b) a salt hydrate having trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. Method of reacting with hydrate, (C) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (D) Mixing trimethylaluminum and triisobutylaluminum, and mixing with a suitable toluene, benzene, ether, etc. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum, and reacting with a salt hydrate having water of crystallization, for example, copper sulfate, hydrate of aluminum sulfate, and heating.

(F) Silica gel or the like is impregnated with water,
A method of treating with triisobutylaluminum and then additionally treating with trimethylaluminum, a method of synthesizing (to)methylalumoxane and isobutylalumoxane by a known method, mixing these two components in predetermined amounts, and reacting by heating. (H) Add a salt having crystal water such as copper sulfate pentahydrate to an aromatic hydrocarbon solvent such as benzene or toluene,
A method of reacting with trimethylaluminum under a temperature of about 40 to 40°C. In this case, the amount of water used is usually 0.5 to 1.
It is 5. The methylalumoxane thus obtained is a linear or cyclic organoaluminum polymer.

<Catalyst Formation> The catalyst of the present invention is obtained by contacting the above-mentioned components (A) and (B) in the polymerization tank or outside the polymerization tank in the presence or absence of the monomer to be polymerized. Can be obtained.

The amounts of the component (A) and the component (B) used in the present invention are arbitrary. For example, in the case of solvent polymerization,
The amount of component (A) used is 10 ⁻⁷ to 1 as a transition metal atom.
It is preferably in the range of 0 ² mmol/l. The molar ratio of Al/transition metal is preferably 100 or more, and particularly preferably 1000 or more.

The catalyst of the present invention comprises components (A) and (B).
Other than the above, it is possible to wrap other components, but as the third component (optional component) that can be added to the components (A) and (B), for example, H ₂ O,
Active hydrogen-containing compounds such as methanol, ethanol and butanol, electron-donating compounds such as ethers, esters and amines, and alkoxy-containing compounds such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane and diphenyldimethoxysilane. It can be illustrated.

When using these catalyst systems for the polymerization of olefins, components (A) and (B) may be introduced separately into the reaction vessel or may have been pre-contacted with components (A) and (B). You may introduce a thing into a reaction tank.

<Use of Catalyst/Polymerization of Olefin> Needless to say, the catalyst of the present invention is applied to solvent polymerization using a solvent, but substantially no solvent is used in liquid phase solventless polymerization or gas phase polymerization. Also applicable to melt polymerization. It is also applied to continuous polymerization and batch polymerization. As a solvent in the case of solvent polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or 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 preferably normal pressure to 50 kg/cm
It is in the range of ^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.

An olefin which is polymerized by the catalyst of the present invention,
That is, the olefin used in the polymerization reaction in the method of the present invention is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
It is an olefin. Specifically, for example, propylene, 1
-Butene, 4-methyl-1-pentene, 1-hexene,
There are 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like, particularly preferably propylene.
These α-olefins can be mixed for use in polymerization.

The catalyst of the present invention can also be copolymerized with the above α-olefins and ethylene. Further, other monomers copolymerizable with the above α-olefin, for example, conjugated and non-conjugated dienes such as butadiene, 1,4-hexadiene, 1,8-nonadiene and 1,9-decadiene, or It is also effective for the copolymerization of cyclic olefins such as cyclopropane, cyclobutene, cyclohexene, norbornene and dicyclopentadiene.

[0036]

[Synthesis of ethylene bis-2-methylindenyl zirconium dichloride]

All reactions were performed under an inert gas atmosphere. The reaction solvent used was previously dried. 500 ml
5.0 g of 2-methylindene in a glass reaction vessel
(33 mmol) was dissolved in 80 ml of tetrahydrofuran,
1.6M hexane solution of n-butyllithium under cooling 2
1 ml was slowly dropped into the reaction vessel. After stirring at room temperature for 1 hour, the mixture was cooled again and 3.1 g of 1,2-dibromoethane
Was slowly added dropwise, and after stirring at room temperature for 12 hours, 50 ml of water was added, and the organic phase was separated and dried. Further, it was washed with heptane several times and dried to obtain 2.9 g of bis-(2-methylindenyl)ethane.

2.1 g (7.3 mmol) of bis-(2-methylindenyl)ethane obtained by the above method was dissolved in 70 ml of tetrahydrofuran, and 9.2 ml of a 1.6M hexane solution of n-butyllithium was added under cooling. It was dripped slowly.
After stirring at room temperature for 3 hours, 1.6 g of zirconium tetrachloride
It was slowly added dropwise to a solution of (7.0 mmol)/60 ml of tetrahydrofuran, stirred for 5 hours, blown with hydrogen chloride gas, and then dried. Subsequently, toluene was added to separate the soluble portion and crystallize at low temperature to obtain 0.95 g of a yellow powder.

The compound obtained is ethylenebis-(2-methylindenyl)zirconium dichloride and both 2-methylindenyl groups are asymmetric, ie the relationship between the substance and the mirror image with respect to the plane containing the zirconium atom. It was confirmed by ¹ HNMR.

[Synthesis of alumoxane] A toluene solution 56 containing 48.2 g of trimethylaluminum in a reaction vessel.
With stirring, 5 g of copper sulfate pentahydrate (50 g) was added at 0° C. to the container at intervals of 5 minutes in an amount of 5 g. After the end, slowly 25
The temperature was raised to 25.degree. C., the temperature was raised to 25.degree. The remaining copper sulfate solid was separated by filtration to obtain a toluene solution of alumoxane. The concentration of methylalumoxane is 27.3 mg/ml (2.7 w/v%)
Met.

[Polymerization] After thoroughly replacing the inside of a stirring autoclave having an internal volume of 1.5 liters with propylene, 500 ml of sufficiently dehydrated and deoxygenated toluene was introduced, and the methylalumoxane synthesized in Example 1 was mixed with Al atoms. 1 in conversion
After introducing 0 mmol and 1.0 mmol of ethylenebis-(2-methylindenyl)zirconium dichloride, propylene was introduced and polymerization was carried out at 20° C. for 15 minutes. Furthermore, by introducing propylene, the internal pressure of the autoclave is 7 kg/cm ² -G
At 40° C. for 2 hours. After the reaction was completed, the obtained polymer slurry was separated by filtration and the polymer was dried. As a result, 56.2 g of polymer was obtained.
The catalytic activity was 308 kg/g-Zr·hour. The number average molecular weight of the polymer was 9.60×10 ⁴ , the molecular weight distribution was 2.02, and the melting point (DSC curve peak temperature) was about 134.
It was 3°C.

Example-1 5.0 g of 2-methylindene used in Reference Example-1
Instead, Kanto Chemical Co., Inc.'s 2,4-dimethylindene
4.76 grams (33 mmol) of
In Consideration-1, 1.6 g of zirconium tetrachloride (7.0 mmmo
except that l) was changed to 7.0 mmol of hafnium tetrachloride.
Ethylene bis (2-me
Cyl-4-methylindenyl) hafnium dichloride
I made it. Furthermore, a reference example using 1 μmol of them-
Polymerization of propylene was carried out under the same conditions as in 1. as a result,
Catalytic activity 54.3 (kg/g-Hf · h), number average molecular weight
Was 14.8×10 ⁴ .

Comparative Example-1 Ethylenebis-(2-methylindenyl)zirconium
Instead of dichloride, ethylene bis (indenyl) di
Same as Reference Example 1 except that ruconium dichloride was used.
Was polymerized. As a result, 80.9 g of polymer was obtained.
Was given. The catalytic activity was 445 kg/g·Zr·hour.
The number average molecular weight of the polymer is 2.13×10 ⁴ , the molecular weight equivalent
The fabric was 2.04 and had a melting point of about 135.2°C. This one too
However, extrusion molding and injection molding were impossible. <Comparative Example-2> The procedure of Reference Example-1 was repeated except that ethylenebis(indenyl)hafnium dichloride was used instead of ethylenebis-(2-methylindenyl)zirconium dichloride. As a result, 12.1 g of polymer was obtained. Catalytic activity 33.6 kg/g-Hf·h, number average molecular weight 1.20×10 ⁵ , molecular weight distribution 2.63, melting point 13
It was 4.8°C.

Example-2 4.3 g of 2-methylindene used in Reference Example-1
Instead, 2,5-dimethylindene manufactured by Kanto Chemical Co., Inc.
Changed to using 4.76 grams (33 mmol)
Except for ethylene bis according to the method of Reference Example 1
-(2-Methyl-5-methylindenyl)zirconium di
Chloride was synthesized. Stirring type with an internal volume of 1.5 liters
After thoroughly replacing the inside of the autoclave with propylene, thoroughly
After introducing 500 ml of dehydrated and deoxygenated toluene,
Al atom conversion of methylalumoxane synthesized in Consideration-1
10 mmol, ethylene bis-(2-
Methyl-5-methylindenyl) zirconium dichloride
Was introduced at a temperature of 20°C.
It was polymerized for 15 minutes. If propylene is introduced,
The internal pressure of the tclave is 40°C when the polymerization pressure is 7 kg/cm ² -G.
It was polymerized for 1 hour. After the reaction was completed, the obtained polymer slurry
The Lee was separated by filtration and the polymer dried. This conclusion
As a result, 50.0 g of a polymer was obtained. Catalytic activity is 17
It was 0 kg/g-Zr·hour. Number average molecular weight of polymer
Was 7.22×10 ⁴ . <Reference Example-2> The procedure of Reference Example-1 was repeated except that 5 ml of 1-hexene was added before the introduction of ethylenebis-(2-methylindenyl)zirconium dichloride. As a result, 51.2
g of polymer was obtained. Catalytic activity is 281 kg/g-Z
It was r·h. The number average molecular weight of the polymer is 7.89×
The polymer had a molecular weight distribution of 10 ⁴ , a molecular weight distribution of 1.90, a hexene content in the polymer of 0.59 mol% and a melting point of 131.4°C.

[0044]

According to the present invention, it is possible to produce a stereoregular polyolefin having a high molecular weight in a high yield, as described above in the section "Means for Solving the Problems".

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-268307 (JP, A) JP-A-4-268308 (JP, A) JP-A-63-66260 (JP, A) Patent 3389265 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (6)

(57) [Claims] 1. A catalyst component for olefin polymerization represented by the following general formula [I]. Ingredient (A) (In the formula, M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and two R are present.
¹ may be the same or different and has 1 to 6 carbon atoms,
It is a monovalent hydrocarbon residue or a hydrocarbon residue containing silicon, and two R ^{2 s that} may be present may be the same or different, and the two adjacent carbon atoms of the 5-membered ring ligand may be combined with each other. A divalent hydrocarbon residue or a silicon-containing hydrocarbon residue having 4 to 20 carbon atoms to be bonded (provided that R ² is butylene;
Group or an unsubstituted 1,3-butadienylene group
Except), R ³ is C1-30, divalent, hydrocarbon residue containing hydrocarbon residues or silicon, X and Y are each independently hydrogen or halogen or a carbon number 1, 20 monovalent hydrocarbon residues or hydrocarbon residues containing nitrogen, oxygen or silicon (provided that
The two five-membered ring ligands bearing the substituents R ¹ and R ² are asymmetric with respect to the plane containing M in terms of their relative position via the group R ^3. ) 2. The catalyst component for olefin polymerization according to claim 1, wherein R ² is methyl-1,3-butadienylene or phenyl-1,3-butadienylene. 3. M is zirconium and R ² is methyl-
The catalyst component for olefin polymerization according to claim 1, which is 1,3-butadienylene. 4. M is hafnium and R ² is methyl-
The catalyst component for olefin polymerization according to claim 1, which is 1,3-butadienylene. 5. The catalyst component for olefin polymerization according to claim 1, wherein M is zirconium and R ² is phenyl-1,3-butadienylene. 6. M is hafnium and R ² is phenyl-
The catalyst component for olefin polymerization according to claim 1, which is 1,3-butadienylene.