JPH06287215A - Homogeneous catalyst for stereoregular olefin polymerization - Google Patents

Abstract

PURPOSE: To provide an improved catalyst which performs efficient polymerization of an α-olefin to form a stereoregular polymer.

CONSTITUTION: There are provided the synthesis of a chiral organozirconium complex for olefin polymerization having the structure of (C₅R'_4-XR)A(C₅ R"_4-YRY)MQP and the use thereof as a pro-catalyst. x and y each represent the number of unsubstituted positions on the cyclopentadienyl ring; R', R", R and R* are each a 1-30C substituted or unsubstituted alkyl, provided that R* is a chiral ligand; A is a fragment containing an element of group IIIb, IVb, Vb or VIb in the periodic table; M is a metal of group IIIa or IVa in the periodic table; and Q is a hydrocarbyl or a halogen group with 3≥p≥0. The complex can be prepared by the alkylation of a dichloride. This complex forms a 'cation-like' species highly reactive in the polymerization of an olefin. A combination thereof with a Lewis acid auxiliary catalyst, propylene and others can perform the polymerization of an α-olefin at very high efficiency and isospecificity.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to improved catalysts and processes using such catalysts, and more particularly to improved chiral catalysts used in stereoregular polymerization of olefins.

[0002]

2. Description of the Related Art A so-called Ziegler-Natta catalyst, which is generally defined as a mixture of a metal alkyl of Group I-III and a transition metal complex of Group III-VIII, is used.
Polymerization and copolymerization of α-olefin and acetylene monomers have already been established in the chemical industry. However, it is of great practical importance if the modification of the catalyst improves the control over the molecular weight and distribution of the molecular weight, eliminates the need for an undesired excessive use of cocatalysts, and allows the stereoregular polymers to be easily prepared. .

There is also a need to control the stereochemistry of a large number of chemicals and polymers, and chiral metal catalysts provide an efficient means of achieving this control.
The design of chiral metal catalysts necessarily involves a suitable ligand that creates an asymmetric (asymmetric) environment around the metal center.
It relies on the design of. Several types of organo (organic) lanthanides which are highly reactive for various reaction purposes are known and are described in US Pat. Nos. 4,668,773 and 4,801,666. . Hydrogenated organic lanthanides (Cp ′ ₂ LnH) ₂ and (Me ₂ S
iCp ″ ₂ LnH) ₂ (Cp ′ = N ₅ (CH ₃ ) ₅
C ₅ , Cp ″ = N ₅ (CH ₃ ) ₄ C ₅ ) is hydrogenated,
It is known to effectively and selectively catalyze many olefin conversions including oligomerization / polymerization, and hydrogen amination. Conventionally, by creating an appropriate coordination environment to carry out asymmetric catalytic conversion centered on metal, extremely fast reaction rate, large production capacity, and reactivity compatible with the specific chiral ligand used. It was not known if the advantageous properties could be obtained. The synthesis of stereoregular polymers is based on chiral organic I with nearly C ₂ symmetry.
Those using group V (Ti, Zr, Hf) catalysts have been reported. Such catalysts have led to isospecific polymerization of α-olefins. Most of these "C _2" catalyst ligand, is based on the indenyl or related cyclopentadienyl component, synthesis is difficult and expensive. Isotacticity of polymer products (specificity of side chain sequence to main chain)
Is in practical use only in very few cases.

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an improved catalyst for the efficient polymerization of .alpha.-olefins to produce stereoregular polymers.

It is a polymerization catalyst that allows better control over the distribution of molecular weight.

Yet another object of the present invention is a polymerization catalyst which, when used with a suitable cocatalyst, allows better control over the desired physical properties of the resulting polymer.

[0007]

The above and other objects of the present invention provide a fixed (chiral) chiral ligand template as described in B below, as opposed to the "C ₂ " symmetric arrangement in A that is commonly found below. Achieved by the features of the present invention which are symmetrically arranged about the coordination region of the metal: The R ^* group is a natural chiral ligand such as menthyl or neomenthyl, which renders the two enantiomers (enantiomers) of B above diastereomers, thereby providing a means for separation. These ligands are enantio-mediated by organolanthanides.
It is known to be effective for selective olefin hydrogenation and hydrogen amination.

[0008]

As shown in the drawings, in the practice of the present invention,
Cyclopentadienyl compounds having a chiral substituent (R ^* ) such as menthyl or neomenthyl (CpR
^* ) Is refluxed with sodium hydride in a polar solvent having a high boiling point such as THF (tetrahydrofuran) to obtain a sodium salt of a cyclopentadienyl compound. This sodium salt is DMSO (dimethyl sulfoxide), dimethylformamide, or preferably T
(CH ₃ ) ₂ AClCp "in polar solvent such as HF
(Cp ″ = C ₅ R _{4 with} R = alkyl group C ₁ -C ₁₂ being preferably methyl), and (CH ₃ ) ₂ SiCl
Yields Cp ″ (CpR ^* ), where A is a bridging element or a fragment containing an element as described below. The bridged chiral cyclopentadienyl has a LiCH ₂ TMS in ambient temperature environment. React with a proton (proton) scavenger such as in an organic, non-polar, aprotic solvent, and then in a polar solvent such as THF or dimethyl ether, MX ₄ (M = Ti, Zr or Hf And X = Cl, Br or I. M
X ₄ is preferably ZrCl ₄ ),
This produces (CH ₃ ) ₂ Si (C ₅ R ₄ ) C ₅ R ^* H ₃ MX ₂ . Halogen is RLi or RMg in a non-polar solvent
Add an alkylating agent such as X to give an alkyl group (C ₁
-C _12, preferably may be substituted with methyl). Addition of Lewis acid cocatalysts such as alumoxane or B (C6 F5) 3 facilitates the polymerization of α-olefins such as propylene. Also, Bronsted acid may be used as an auxiliary catalyst. Suitable Bronsted acids that can be used have the formula HY ⁺ Z ⁻ . Where Y ⁺ is N (R
^{1 R2} R ^{3) +,} where Vb or VIb of R ^1, R ² and R ³ are the Periodic Table with an alkyl group (C ₁ -C _12), the form of
Fragments containing group III elements, Z ⁻ are fragments containing group IIIb elements. Examples of such acids include HN
^{_{(CH 3) 3 + B (}} C 6 F 5) 4 -; HN (CH 3) 3
⁺ Al (C ₆ F ₅ ) ₄ ⁻ or HP (CH ₃ ) ₃ ⁺ B
(C ₆ F ₅ ) ₄ ⁻ is included. The catalyst thus prepared is (C ₅ R ' _4-X R ^* _X ) A (C ₅ R "
_4-Y R '" _Y ) MQ _P , where x and y represent the number of unsubstituted positions on the cyclopentadienyl ring;
R ', R ", R'" and R ^* represent an alkyl group having 1 to 30 carbon atoms, R ^* is a chiral ligand; A is a group IIIb, IVb, Vb or VIb of the periodic table. Fragments containing elements, preferably Si; M is IIIa, IV of the Periodic Table
a or a Va group metal, preferably Zr; and Q is 3
Hydrocarbyl, aryl, and halogen groups with ≧ p ≧ 0. Alternatively, Q may be a mixture of hydrocarbyl, aryl or halogen groups; where Q is Q ', Q "and optionally Q'" at p = 1.

By varying the chiral ligand (R ^* ), the physical properties of the resulting polymer can be tailored as desired. Also, varying A affects the solubility and other properties of the catalyst.

R ', R "and R'" may be hydrogen or hydrocarbyl groups. Examples of hydrocarbyl groups that can be used include alkyl, alkenyl, aryl, alkylaryl, arylalkyl groups. More specifically, examples of hydrocarbyl groups include methyl, ethyl,
n-propyl, isopropyl, butyl, tert-butyl,
Examples include amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, methylene, ethylene, propylene, and other similar groups.

A is a catalyst fixed in three dimensions (stereo rigid)
Therefore, it is a stable component such as an element bridging two (C ₅ (R) ₄ ) rings or a fragment containing the element. The elements in A are IIIb, IVb, Vb, and V of the periodic table.
You can choose from the Ib group. Examples of A include Si and G
e, S, C, Sn, Pb, B, Al, Ga, In, T
l, N, P, As, Sb, Bi, Se, and Te are included. Preferred A is a Si (CH _{3) 2,} elements alkyl or aryl group, provided that C = 1-30, may have.

Similarly, Q can be any of the hydrocarbyl groups described above for R, but is preferably hydrogen, most preferably chlorine. Also in a preferred embodiment, p
Is 2.

The metallocene catalyst must be chiral and must not have C ₂ -based symmetry, ie the mirror image, in order to polymerize propylene or higher α-olefins to give useful polymer products. Must not be stackable on top of each other. It has been discovered that the chiral nature of the metallocene catalyst provides stereochemical control over the polymer product as well as the production of high isotactic index polymers. Also, the catalyst should be sterically fixed to help control the stereochemistry of the polymerization.

The catalyst system of the present invention also includes a Lewis acid catalyst in combination with a metallocene catalyst. Lewis acid catalysts in the case of annular general formula _{(R-Al-O) n} , preferably the case of linear alumoxane represented by the general formula R (R-Al-O-) n -AlR 2. Here, R has a carbon number of 1-
An alkyl group, preferably 5, and n is an integer, preferably 1 to about 20. Most preferred for R is a methyl group. Alternatively, triarylborane compounds such as B (C ₆ F ₅ ) ₃ can also be used.

[0015]

【Example】

Ingredients and methods All work is done with a double-manifold Schlenk.
In a flame-fired Schlenk-type glass container placed in a line or connected to a high vacuum (10 ^-5 torr) system, or in a nitrogen-filled glove box equipped with a high-volume atmospheric recirculator, oxygen It was performed by strictly removing water.
Argon, ethylene, propylene, dihydrogen and deuterium gases were purified through a MnO supported oxygen scavenging column and a molecular sieve column. The aliphatic hydrocarbon solvent was pretreated with concentrated H ₂ SO ₄ , KMnO ₄ solution, MgSO ₄ , and Na + 4A molecular sieves. All reaction solvents are Na / K under nitrogen
/ Benzophenone is distilled from, after concentration, was stored in a small amount of _{[Tiη- (C 5 H 5)} 2 Cl] in the vacuum bulbs on a vacuum line comprising ₂ ZnCl ₂ as an indicator. Toluene, cyclohexane, and heptane undergo an addition vacuum transition to Na / K to give at least 1 prior to use in catalytic experiments.
It was stirred for a day. The olefin was purified by stirring against Na / K for at least 6 hours and then vacuum transferred anew. The deuterated solvent was dried over Na / K alloy and vacuum transferred before use.

Tetramethylcyclopentadiene is an "Org
anometallics ", a. complex prepared according to the procedure described in 1984,3,819-821 and (trimethylsilyl) methyl lithium (LiCH ₂ TMS) 2
-Lithium-mesitylene was also prepared by procedures well known in the art.

Example 1 Preparation of CP ₂ Intermediate (CH ₃ ) ₂ SiCp ″ H (+) CHNMCpH 7.76 g (36.15 mmo) in 120 ml of THF.
l) Me ₂ SiClCp ″ and 9.0 g (39.76 m
A suspension of (mol) Na ⁺ (C ₅ H ₅ NM) ⁻ (NM = neomenthyl) was stirred for 12 hours at ambient temperature. Then the solvent was removed. Then 200 ml of solution
After liberal extraction with pentane and filtering the mixture, the solvent is removed in vacuo to give (CH ₃ ) ₂ as a clear colorless oil.
SiCp ″ H (+) CHNMC pH was quantitatively generated.

Example 2 (CH ₃ ) ₂ SiCp "H (-) (MCp) H 7.76 g (36.15 mmo) in 120 ml of THF.
l) Me ₂ SiClCp ″ and 9.0 g (39.16 m
A suspension of (mol) Na ⁺ (C ₅ H ₅ M) − (M = menthyl) was stirred for 12 hours at ambient temperature. Then the solution was extracted with 200 ml of pentane and the mixture was filtered. The solvent was removed in vacuo, a clear colorless oil _{(CH 3) 2 SiCp "H} (-) were quantitated generated (18.22 g) and MCPH.

Example 3 Preparation of Chiral Li Intermediate (CH ₃ ) ₂ SnCp ″ (+) NMCpLi _{2 In} 120 ml of THF, (CH ₃ ) 2 SnClCp ″ and Na ⁺ (C ₅ H ₅ NM) ⁻ (1: 1 mol) The (ratio) -dissolved suspension was stirred for 12 hours at ambient temperature. 2 equivalents of Li
CH ₂ TMS was added and stirred in pentane solution. The pentane was removed, the residue was extracted and filtered, then the solvent was removed to yield (CH ₃ ) ₂ SnCp ″ (+) NMCpLi ₂ .

Example 4 (CH ₃ ) ₂ GeCp "(+) NMCpLi ₂ 120 ml of THF was charged with (CH ₃ ) ₂ GeClCp and N _2.
The suspension of a ⁺ (C ₅ H ₅ NM) ⁻ (1: 1 molar ratio) was stirred for 12 hours at ambient temperature. LiCH ₂ TM
S 2 was added and stirred in pentane solution. The pentane was removed, the residue was extracted with THF and filtered, then the solvent was removed as in Example 3 (CH ₃ ) ₂ GeCp ″ (+) NM.
CpLi ₂ was produced.

Example 5 (CH ₃ ) ₂ SiCp ″ (C ₂ H ₅ ) CpLi ₂ (CH ₃ ) ₂ SiClCp and N in 120 ml of THF.
^{_{a + (C 5 H 4 C}} 2 H 5) - The suspension dissolved, and stirred for 12 hours at ambient temperature. LiCH ₂ TMS was added and stirred. After removing the solvent and extracting the residue and filtering, the solvent was removed as in Example 3 to remove (CH ₃ ) ₂ SiCp ″ (C
₂ H ₅ ) CpLi ₂ was produced.

Example 6 Synthesis of (CH ₃ ) ₂ SiCp ″ (+) NMCpLi _{2 To} the reaction product of Example 1 was added 6.6 g of LiCH ₂ TMS in 250 ml of ambient temperature pentane and the mixture was left for 24 hours. Stir the solvent in vacuo and remove 1
6.75 g of finely crystalline solid was produced.

Example 7 Synthesis of (CH ₃ ) ₂ SiCp ″ (−) NMCpLi _{2 To} the reaction product of Example 2 was added 6.6 g of LiCH ₂ TMS in 250 ml of ambient temperature pentane and the mixture was allowed to stand for 24 hours. Stir the solvent in vacuo and remove 1
6.75 g of finely crystalline solid was produced.

Example 8 Preparation of Chiral Zirconium Catalyst (CH ₃ ) ₂ Si (CH ₃ ) ₄ C ₅ ) [(+) NMC ₅
Synthesis of H ₃ ] ZrCl ₂ (CH ₃ ) ₂ SiCp ″ (+) NMCpLi ₂ and ZrC
l ₄ was combined in THF at a molar ratio of 1: 1 to give 6
The mixture was stirred at 0 ° C for 18 hours. After removing the solvent in vacuum,
Chiral zirconium dichloride was extracted and diluted with pentane. After concentration, the obtained solution was gradually cooled to obtain a zirconocene complex as a fine crystalline solid.

Example 9 (CH ₃ ) ₂ Si (Cp ″) [(+) NMCp] Zr
Synthesis of (CH ₃ ) ₂ The above dichloride complex was reacted with methyllithium in toluene to obtain the corresponding dimethyl complex.

The dimethyl or dichloride complex is 1.
It can be converted to the corresponding cationic olefin polymerization catalyst by reacting with 0 equivalent of B (C ₆ F ₅ ) ₃ or 500 to 1000 equivalents of methylalumoxane.

Example 10 Polymerization of Olefin Under strictly anaerobic conditions 8 mg of (CH ₃ ) ₂ Si
(Cp ") [(+) NMCp] Zr (CH 3) 2 and 10
Add mg of B (C ₆ F ₅ ) ₃ to the flask and add 50 ml.
Dissolved in pentane; the inside of the flask container was evacuated and filled with propylene gas. The reaction was carried out at ambient temperature and pressure. Polymerization started immediately and was monitored using a pressure gauge. At the end, polymerization was extinguished by adding acidified aqueous methanol solution to obtain polypropylene. The portion insoluble in methanol (> 90% of the product) was highly crystalline, and was 97% overall by ¹³ C NMR spectroscopy.
% Isotactic.

Example 11 Copolymerization of Olefin Under strictly anaerobic conditions, 8 mg of (CH ₃ ) ₂ Si
(Cp ″) [(+) NMCp] Zr (CH ₃ ) ₂ and 1 molar equivalent of B (C ₆ G ₅ ) ₃ were placed in a flask and the volume was adjusted to 50 m.
It was dissolved in 1 l of pentane; the inside of the flask container was evacuated and filled with a mixed gas of propylene and butene 50/50. The reaction was carried out at temperatures ranging from -20 ° C to -40 ° C and at ambient pressure. Polymerization started immediately and was monitored using a pressure gauge. At the end, polymerization was extinguished by adding an acidified aqueous methanol solution to obtain a random propylene-butylene copolymer. The portion insoluble in methanol (> 90% of the product) had high crystallinity, and ¹³ C NMR spectrum analysis revealed that it was highly isotactic overall. First, react in an atmosphere of 100% propylene,
After that, if the reaction is carried out in an atmosphere of 100% butene and the reaction is finally extinguished, block copolymerization can be carried out.

Example 12 Olefin Dimerization Under strictly anaerobic conditions, 8 mg of (CH ₃ ) ₂ Si
Into a flask containing (Cp ″) [(+) NMCp] Zr (CH ₃ ) ₂ was injected 50 ml of pentane; the inside of the flask vessel was evacuated and charged with isobutylene. The polymerization reaction was carried out at ambient temperature and pressure. The dimerization started immediately and was monitored using a pressure gauge, at the end of which the acidified aqueous methanol solution was added to quench the dimerization and form the dimer.

Example 13 Hydrogenation of an Olefin Under strictly anaerobic conditions 8 mg of (CH ₃ ) ₂ Si
(Cp ") [(+) NMCp] Zr (CH 3) 2 and 50
In a flask containing 0 equivalents of methylalumoxane, 50
ml of pentane was injected; the inside of the flask vessel was evacuated and filled with propylene gas and hydrogen gas in a ratio of 1: 1. The hydrogenation started immediately and could be monitored with a pressure gauge until the end.

Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various modifications can be made without departing from the scope of the invention and that the constituent elements of the invention can be replaced with equivalents. Would be obvious. Further, based on the teaching of the invention, without departing from the essential scope of the invention,
Many modifications may be made to suit a particular situation or raw material. Therefore, the present invention is not limited to the particular embodiments disclosed as what are considered to be the best mode presently set forth for carrying out it, and the embodiments and equivalents falling within the scope of the claims It includes everything.

The individual features of the invention are set forth in the appended claims.

[0033]

As described above, according to the present invention, α
-Effective polymerization of olefins to produce stereoregular polymers, and when used with co-catalysts, provides better control over the resulting polymer's molecular weight, molecular weight distribution, and desired physical properties. A possible polymerization catalyst is obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing the synthesis of the catalyst of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihiro Yamamoto No. 4 Dee 1740, Evanston, Hinman, 60201, Illinois, USA (72) Inventor Lorent, Bullard, Pennsylvania, USA 19104, Philadelphia, Wallnut Street, Number 710 2300 (72) Inventor Michael, Jardero, California 91107, Pasadena, Apartment 217, Edermar 2386

Claims (37)

[Claims] 1. A catalyst used in the polymerization and copolymerization of an α-olefin, the catalyst having a composition represented by the following formula: (C ₅ R ′ _4-X R ^* _X ) A (C ₅ R " _4-Y R '" _Y ) MQ
_P where x and y represent the number of unsubstituted positions on the cyclopentadienyl ring; R ′, R ″, R ′ ″ and R ^* are carbon atoms 1-
30 represents a substituted or unsubstituted alkyl group or hydrogen, R
^* Has a chiral substituent; A is IIIb of the periodic table,
Fragments containing elements of group IVb, Vb or VIb;
M is a metal of group IIIa, IVa or Va of the periodic table; and Q is a hydrocarbyl group, an aryl group or a halogen group of 3 ≧ p ≧ o. 2. The catalyst of claim 1, wherein R ^* is selected from the group consisting of menthyl, neomenthyl, or phenylmenthyl. 3. The A is C, Ge, Sn, P, N, B,
The catalyst according to claim 1, which is selected from a fragment containing an element selected from the group consisting of Si. 4. The catalyst according to claim 1, wherein A is a fragment containing silicon. 5. M is Zr, Hf, Ti, Sc, V,
The catalyst of claim 1 selected from the group consisting of Nd, Ta, Y, or La. 6. The catalyst according to claim 1, wherein M is zirconium. 7. The Q is hydrogen or 1-12 carbon atoms.
The catalyst according to claim 1, which is an alkyl group of 8. The catalyst according to claim 1, wherein Q is selected from the group consisting of a hydrogen group, an aryl group, an alkyl group, and a mixed group thereof. 9. The catalyst according to claim 1, wherein the catalyst composition is added to a Lewis acid as a cocatalyst to form an efficient catalyst in the polymerization reaction. 10. The Lewis acid is alumoxane or B.
(C ₆ F _{5) 3} in claim 9, wherein the catalyst selected from the group. 11. The catalyst according to claim 1, wherein the catalyst composition is added to Bronsted acid as a cocatalyst to form an efficient catalyst in the polymerization reaction. 12. The catalyst composition is a Bronsted acid of the formula HY ⁺ Z ⁻ , wherein Y ⁺ is N (R ¹ R ² R ³ ) ⁺ ,
However, R ¹ , R ² and R ³ are alkyl groups (C ₁ -C ₁₂ ),
The catalyst according to claim 1, which is added to a fragment containing an element of group Vb or VIb of the periodic table in the form of Z-, wherein Z ^- is a fragment containing an element of group IIIb. 13. The Brnsted acid is HN (CH
^{_{3) 3 + B (C 6}} F 5) 4 -, HN (CH 3) 3 + Al
(C ₆ F _{5) 4} ^- or ^{_{HP (CH 3) 3 + B}} (C 6
F _{5) 4} ^- selected from the group consisting of claims 11, wherein the catalyst. 14. A catalyst system used in the polymerization and copolymerization of α-olefins, comprising a catalyst having a component represented by the formula: (CpR ^* ) A (Cp ″) MQ _P, provided that Cp and Cp ″ each represent a substituted or unsubstituted cyclopentadienyl ring; R ^* is a substituted or unsubstituted alkyl group having a chiral substituent (C = 1-3
0); A is a fragment containing an element of group IIIb, IVb, Vb or VIb of the periodic table; M is III of the periodic table
a, IVa or Va group metal; and Q is a hydrocarbyl group or halogen group with 3 ≧ p ≧ o. 15. The R ^* is menthyl, neomenthyl,
15. The catalyst system of claim 14 selected from the group consisting of phenylmenthyl. 16. The A is C, Ge, Sn, P, N,
15. A catalyst system according to claim 14 selected from the group consisting of B or Si containing fragments. 17. The catalyst system according to claim 14, wherein the A is Si (CH ₃ ) ₂ . 18. The M is Zr, Hf, Ti, Sc,
15. The catalyst system of claim 14, selected from the group consisting of V, Nd, Ta, Y, or La. 19. The M is zirconium.
4. The catalyst system according to 4. 20. The Q is hydrogen or has 1-1 carbon atoms.
15. The catalyst system of claim 14 which is 2 alkyl groups. 21. The method according to claim 14, further comprising an activated catalyst.
The catalyst system described. 22. A method for preparing a catalyst used to polymerize olefins, comprising: 1) a cyclopentadienyl anion having a chiral substituent in a polar solvent, a substituent AR ₂ X, where A is cyclic. A step of combining with a cyclopentadienyl compound having IIIb, IVb, Vb or VIb group element in the table, R is an alkyl group (C ₁ -C ₁₂ ), and X is hydrogen; Mixing the product of step 1 with a proton scavenger in a non-polar solvent; 3) mixing the product of step 2 in a polar solvent with MX ₄ , where M = metal of group IIIa, IVa or Va of the Periodic Table. so,
X is mixed with hydrogen; and 4) a step of separating the chiral catalyst complex from the product of step 3 by mixing the product of step 3 with a non-polar solvent and extracting the non-polar solvent. A method including; 23. The method of claim 22, wherein the cyclopentadienyl anion having a chiral substituent is prepared by refluxing a cyclopentadienyl compound having a chiral substituent with NaH in a polar solvent. . 24. The method of claim 22, wherein the anion of Step 1 is combined with the compound in THF at ambient temperature. 25. The proton removing agent is LiCH ₂ TMS.
23. The method of claim 22, wherein 26. The method of claim 22, wherein the product of Step 2 is mixed with the proton scavenger at ambient temperature. 27. The method of claim 22, wherein the chiral catalyst complex is alkylated. 28. The method of claim 22, wherein the chiral catalyst complex is methylated. 29. In the method for polymerizing an α-olefin, 1) in a step of dissolving a catalyst and a Lewis acid in a non-polar solvent in a container, the catalyst is represented by the following formula: (C5 R ′ _{4- X} R ^* _X ) A (C ₅ R " _4-Y R '" _Y ) MQ
_P where x and y represent the number of unsubstituted positions on the cyclopentadienyl ring; R ′, R ″, R ′ ″ and R ^* are carbon atoms 1-
30 represents a substituted or unsubstituted alkyl group or hydrogen, R
^* Has a chiral substituent; A is IIIb of the periodic table,
Fragments containing elements of group IVb, Vb or VIb;
M is a metal of group IIIa, IVa or Va of the periodic table; and Q is a hydrocarbyl group or a halogen group of 3 ≧ p ≧ 0; 2) a step of filling the container with α-olefin; 3) a polymerization reaction And a step of 4) erasing the polymerization reaction at the end. 30. The method according to claim 29, wherein R ^* represents an alkyl group selected from the group consisting of menthyl, neomenthyl and phenylmenthyl. 31. The Lewis acid is alumoxane or B.
(C ₆ F ₅₎ The method of claim 29 wherein the _3. 32. The method of claim 29, wherein said A is Si (CH _{3) 2} . 33. The method of claim 29, wherein M is Zr. 34. In the method for hydrogenating an olefin, 1) in the step of dissolving the catalyst in a non-polar solvent in a container, the catalyst is represented by the following formula: (C ₅ R ′ _4-X R ^* _X ) A (C ₅ R " _4-Y R '" Y) MQ
_P where x and y represent the number of unsubstituted positions on the cyclopentadienyl ring; R ′, R ″, R ′ ″ and R ^* are carbon atoms 1-
30 represents a substituted or unsubstituted alkyl group or hydrogen, R
^* Has a chiral substituent; A is IIIb of the periodic table,
Fragments containing elements of group IVb, Vb or VIb;
M is a metal of group IIIa, IVa or Va of the periodic table; and Q is a hydrocarbyl group or a halogen group of 3 ≧ p ≧ 0; 2) a step of adding an olefin to the container; 3) H _{2 in the} container A step of adding a gas; and 4) a step of advancing a hydrogenation reaction to produce a hydrogenated olefin. 35. The method according to claim 34, wherein R ^* represents an alkyl group selected from the group consisting of menthyl, neomenthyl and phenylmenthyl. 36. The method of claim 34, wherein said A is Si (CH ₃ ) ₂ . 37. The method of claim 34, wherein M is Zr.