JP3337905B2 - New chiral metallocene compound, method for synthesizing the same, and method for polymerizing olefin using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel chiral metallocene compound, a method for synthesizing the same, and a method for polymerizing an olefin using the compound. More specifically, the present invention relates to a metallocene compound having a specific structure, a method for synthesizing the same, and a method for polymerizing an olefin using the metallocene compound.

[0002]

2. Description of the Related Art As a homogeneous catalyst for olefin polymerization
Are well known metallocene compounds. Through
Polymerization of olefins using ordinary metallocene compounds
The method, especially the method of stereoregular polymerization of α-olefin,
Since reported by W. Kaminsky et al. (Angew. Chem.,9
7, 507 (1985)). These breaks
Good examples include some of the hydrogens in the cyclopentadienyl group.
Of the polymer obtained by the method of substituting
Attempts to improve the rule are common (Yamazaki et al.
Chemistry Letters, 1853 (1989), JP-A-4-26830
No. 7).

[0003] In addition, many attempts have been reported to improve the stereoregularity of olefin polymers by metallocene compounds having an ethylene bridged bisindenyl derivative as a ligand (eg, Organometallics, 13 , 954).
(1994), J. Organmet. Chem., 288 , 63 (1985)), but the polymerization of olefins with these metallocene compounds has high activity, but the stereoregularity of the obtained polyolefin is not sufficient. . In addition, in many cases, these metallocene compounds are obtained in the synthesis stage as an equal mixture of not only a racemic form which gives a stereoregular polyolefin but also a meso form which gives an atactic polymer. Therefore, in order to carry out stereoregular polymerization of olefins using these metallocene compounds, removal of the meso form is indispensable, which is economically disadvantageous.

[0004] The racemate is an equal mixture of two diastereomers and is not substantially an optically active metallocene compound. On the other hand, attempts have been made to synthesize an optically active metallocene compound containing only one diastereomer without a meso form (Burk, MJ et al., Organometall
ics, 10 , 2998 (1991)). This chiral metallocene compound has not been applied to the polymerization of olefins, but has been applied to asymmetric reactions in organic synthesis (Halterman, RL et al., J. Org. Ch.
em., 59 , 2642 (1994)), and is expected to be applied not only to olefin polymerization but also to organic synthetic chemistry.

[0005]

According to the above-mentioned method, in many cases, a metallocene compound produces both a racemic form and a meso form component in a synthesis step, separates them, and forms a racemic form as an olefin polymerization catalyst. In addition, some metallocene compounds give highly active and highly stereoregular polyolefins, but also a new chiral metallocene compound catalyst system that gives highly active and highly stereoregular polyolefins. It would be desirable to develop synthetic methods that do not require separation of both body components. Further, in the polymerization of α-olefin, the stereoregularity of the obtained poly α-olefin is important, and if the structure of such a catalyst is predicted in advance, it is extremely useful industrially.

[0006]

Means for Solving the Problems The present inventors have solved the above problems, and have earnestly studied a novel chiral metallocene compound which gives a highly active and highly stereoregular polyolefin, a method for synthesizing the same, and a polymerization method using the same. After examination, the present invention was completed.

That is, the present invention provides a compound represented by the following general formula [1]:
Is a novel chiral metallocene compound represented by the formula:

[0008]

Embedded image ( Wherein C ¹ and C ² represent asymmetric carbons, and R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, and have 1 to 20 carbon atoms.
Linear alkyl group, branched alkyl having 3 to 20 carbon atoms
Group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, a linear alkoxy group having 1 to 20 carbon atoms,
A branched alkoxy group having 3 to 20 carbon atoms, 3 to 20 carbon atoms
Cyclic alkoxy group, aryloxy having 6 to 20 carbon atoms
Group, a silicon-containing alkyl group, and R ¹⁰ has 1 carbon atom.
-20 linear alkyl group, branched alkyl group having 3-20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
Alkoxy group, selected from a silicon-containing alkyl group, also, R ¹
And R ² and R ³ and R ⁴ are different from each other, and the asymmetric carbon C ¹ and C ²
Is represented by R, S notation (R, R) or (S,
S) or a mixture of (R, R) and (S, S).
R ^{5 to} R ⁹ may be such that R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are directly bonded to each other to form the same cyclic hydrocarbon substituent; M is a metal selected from Group 4 of the periodic table, Y is bonded to C ¹ and C ² atoms, and methylene,
Dimethylmethylene, diphenylmethylidene Ren, Jimechirushiri
X is selected from the group consisting of
Is selected from a halogen, an alkyl group or an anionic ligand, n is 0 or 1, and m is an integer of 1 or 2. )

Further, the present invention provides a method for producing a chiral compound represented by the following general formula [3] by reacting a chiral compound represented by the following general formula [2] with a trihalomethanesulfonic acid derivative. And the following general formula [4]
To a chiral compound of the following general formula [5] (Chemical Formula 10), and then a dialkali metal salt of the compound is converted to a general formula MXn (M is a metal selected from Group 4 of the periodic table; Is a halogen, and n is an integer of 3 or 4.) or the MXn ether complex, and a method for synthesizing a novel chiral metallocene compound according to claim 1.

[0010]

Embedded image ( Wherein C ¹ and C ² represent an asymmetric carbon, and R ¹ , R ² , R ³ and
And R ⁴ are hydrogen, a linear alkyl group having 1 to 20 carbon atoms,
A branched alkyl group having a prime number of 3 to 20, a ring having a carbon number of 3 to 20
Alkyl group, aryl group having 6 to 20 carbon atoms, 1 carbon atom
To 20 linear alkoxy groups, 3 to 20 carbon atoms, branched
Alkoxy group, cyclic alkoxy group having 3 to 20 carbon atoms, carbon
Aryloxy group having 6 to 20 prime numbers, silicon-containing alkyl
Selected from group and, R ¹ and R ² and R ³ and R ⁴ are different from each other, the configuration of the asymmetric carbon C ¹ and C ² are, R, S-notation (R, R) or (S, S ) Or a mixture of (R, R) and (S, S), OH represents a hydroxy group, Y is bonded to C ¹ and C ² atoms, and methylene, dimethyl
Lmethylene, diphenylmethylene, dimethylsilylene,
Selected from diphenylsilylene, and n is 0 or 1. )

[0011]

Embedded image ( Wherein C ¹ and C ² represent an asymmetric carbon, and R ¹ , R ² , R ³ and
And R ⁴ are hydrogen, a linear alkyl group having 1 to 20 carbon atoms,
A branched alkyl group having a prime number of 3 to 20, a ring having a carbon number of 3 to 20
Alkyl group, aryl group having 6 to 20 carbon atoms, 1 carbon atom
To 20 linear alkoxy groups, 3 to 20 carbon atoms, branched
Alkoxy group, cyclic alkoxy group having 3 to 20 carbon atoms, carbon
Aryloxy group having 6 to 20 prime numbers, silicon-containing alkyl
Selected from group and, R ¹ and R ² and R ³ and R ⁴ are different from each other, the configuration of the asymmetric carbon C ¹ and C ² are, R, S-notation (R, R) or (S, S ) Or a mixture of (R, R) and (S, S), L is a trihalomethanesulfonyl group, Y is bonded to C ¹ and C ² atoms,
Dimethyl methylene, diphenyl methylene, dimethyl
Selected from silylene and diphenylsilylene
And n is 0 or 1. )

[0012]

Embedded image ( Wherein , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, having 1 to 1 carbon atoms)
20 straight-chain alkyl groups, branched alkyl groups having 3 to 20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
R ¹⁰ is selected from a xy group and a silicon-containing alkyl group,
Number 1 to 20 linear alkyl group, C 3 to C 20 branched
Alkyl group, cyclic alkyl group having 3 to 20 carbon atoms, carbon number
6-20 aryl groups, linear alcohols having 1-20 carbon atoms
Xy group, branched alkoxy group having 3 to 20 carbon atoms, carbon number
Cyclic alkoxy group having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms
Roxy group, selected from silicon-containing alkyl group, R ¹⁰ is
1 to 20 carbon atoms linear alkyl group, 3 to 20 carbon atoms
Cyclic alkyl group, cyclic alkyl group having 3 to 20 carbon atoms, carbon
An aryl group having 6 to 20 primes, a linear a
Alkoxy group, branched alkoxy group having 3 to 20 carbon atoms, carbon
A cyclic alkoxy group having a prime number of 3 to 20, an alkoxy group having a carbon number of 6 to 20;
Selected from a reeloxy group and a silicon-containing alkyl group , and R ^{5 to} R ⁹ are R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R
⁸ and R ⁹ may be directly bonded to each other to form the same cyclic hydrocarbon substituent, and K is selected from alkali metals. )

[0013]

Embedded image ( Wherein C ¹ and C ² represent asymmetric carbons, and R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, and have 1 to 20 carbon atoms.
Linear alkyl group, branched alkyl having 3 to 20 carbon atoms
Group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, a linear alkoxy group having 1 to 20 carbon atoms,
A branched alkoxy group having 3 to 20 carbon atoms, 3 to 20 carbon atoms
Cyclic alkoxy group, aryloxy having 6 to 20 carbon atoms
Group, a silicon-containing alkyl group, and R ¹⁰ has 1 carbon atom.
-20 linear alkyl group, branched alkyl group having 3-20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
Alkoxy group, selected from a silicon-containing alkyl group, also, R ¹
And R ² and R ³ and R ⁴ are different from each other, and the asymmetric carbon C ¹ and C ²
Is represented by R, S notation (R, R) or (S,
S) or a mixture of (R, R) and (S, S).
R ^{5 to} R ⁹ may be such that R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are directly bonded to each other to form the same cyclic hydrocarbon substituent; Y is bonded to C ¹ and C ² atoms,
Methylene, dimethylmethylene, diphenylmethylene, di
Methylsilylene, those selected from the group consisting of diphenyl silicon-les-down
And n is 0 or 1. )

Further, the present invention is a method for polymerizing an olefin, comprising polymerizing an olefin using the metallocene compound represented by the above general formula [1].

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, C ¹ and C ² in the above general formulas [1], [2], [3] and [5] are asymmetric carbons. All atoms or substituents that are directly bonded are different atoms or substituents. That is, R ¹ and R ² directly bonded to C ¹ which is an asymmetric center in the general formula [1] are different. Similarly, R ³ and R ⁴ bonded to C ² are different. Also, in order for the metallocene compound represented by the general formula [1] to have optical activity, the configuration of the asymmetric carbons C ¹ and C ² must be (R, R) or (S, S) in R, S notation. ),
Or a mixture of (R, R) and (S, S).

In the present invention, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ are hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 3 carbon atoms. To 20 cyclic alkyl groups, aryl groups having 6 to 20 carbon atoms, linear alkoxy groups having 1 to 20 carbon atoms, branched alkoxy groups having 3 to 20 carbon atoms, cyclic alkoxy groups having 3 to 20 carbon atoms, carbon atoms It is selected from aryloxy groups of formulas 6 to 20, and silicon-containing alkyl groups. Examples of the straight-chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups, and a branched alkyl group. Examples include isopropyl, 2-methylpropyl, tert-butyl or neopentyl group, and the cyclic alkyl group includes cyclopropyl, cyclopropylmethyl, cyclobutyl,
Examples include cyclobutylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, norbornyl, norbornylmethyl, benzyl or menthyl groups.

Examples of the aryl group include phenyl, toluyl, xyyl, naphthyl and anthryl.

As the linear alkoxy group, methoxy,
Ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptoxy groups, and the like.Examples of the branched alkoxy group include isopropoxy, 2-methylpropoxy, tert-butoxy and neopentoxy group, and the like as the cyclic alkoxy group. , Cyclopropoxy, cyclopropylmethoxy, cyclobutoxy, cyclobutylmethoxy, cyclopentoxy, cyclopentylmethoxy, cyclohexyloxy, cyclohexylmethoxy, norboniloxy, norbornenemethoxy, benzyloxy or mentoxy groups.

As the aryloxy group, phenoxy,
Examples include tolyloxy, xyloxy, naphthoxy or anthroxy groups.

Examples of the silicon-containing alkyl group include a trimethylsilyl, dimethylethylsilyl, diphenylmethylsilyl, cyclohexyldimethylsilyl, norbornyldimethylsilyl, triphenylsilyl or 2- (methyldiphenylsilyl) ethyl group.

In the present invention, the above general formula [1],
R in [4] and [5]^Five~ R⁹Is R ^FiveAnd R⁶, R⁶When
R⁷, R⁷And R⁸Or R⁸And R⁹Are directly connected to each other
One cyclic hydrocarbon substituent may be formed. concrete
R^FiveAnd R⁶Ie the [g or e] -position, R⁶When
R⁷, Ie the [f] -position, R⁷And R⁸, That is, [e
Or g] -position, or R⁸And R⁹, Ie [cd] -position
Are linked together by a cyclic hydrocarbon substituent
, Cyclohexa, cyclohepta, benz
Or naphtha-indenyl groups and their derivatives.
It is.

The above general formulas [1], [2] and [3]
And Y in [5] bonds to C ¹ and C ² atoms, and specific examples thereof include methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, and diphenylsilylene.

In the present invention, M in the general formula [1] is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium. X is selected from halogen, an alkyl group or an anionic ligand; halogen is selected from fluorine, chlorine, bromine and iodine; and the alkyl group is methyl,
Examples include linear alkyl such as ethyl and propyl, branched alkyl such as isopropyl, and cyclic alkyl such as cyclopropyl. Further, as the anionic ligand, an organic phosphorus compound such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine, or methoxy, ethoxy, n-butoxy, sec-butoxy, tert-butoxy, phenoxy, or naphthoxy Or an ether compound such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane.

In the present invention, L in the above general formula [3] is a trihalomethanesulfonyl group, such as a trifluoromethanesulfonyl, trichloromethanesulfonyl or tribromomethanesulfonyl group. Further, K in the general formula [4] is selected from alkali metals, and lithium, sodium or potassium is particularly preferably used.

In the present invention, the trihalomethanesulfonic acid derivative used for converting the chiral compound represented by the above general formula [2] into the chiral compound of the above general formula [3] includes, for example, trifluoromethanesulfonic acid. , Trifluoromethanesulfonic anhydride, trifluoromethanesulfonyl chloride, trichloromethanesulfonic acid, trichloromethanesulfonic anhydride, trichloromethanesulfonyl chloride, tribromomethanesulfonic acid, tribromomethanesulfonic anhydride or tribromomethanesulfonyl bromide, etc. Is mentioned. Particularly preferably, trihalomethanesulfonic anhydride is used.

In the reaction of a diol, which is a chiral compound represented by the above general formula [2], with a trihalomethanesulfonic acid derivative, 2 moles or more of the trihalomethanesulfonic acid derivative is added to 1 mole of the diol, and the Lewis base is added. Into the chiral compound of the above general formula [3] in the presence of As the Lewis base used, amines and pyridines are particularly preferable, and the Lewis base is used in a range of 0.5 to 5 equivalents to the trihalomethanesulfonic acid derivative, and particularly preferably in the coexistence of 1 to 3 equivalents. Perform the reaction. Examples of amines and pyridines to be used include triethylamine, aniline, pyridine, lutidine and the like. This reaction is carried out without a solvent or in an organic solvent inert to the reaction, and the reaction temperature is -90.
It is performed in the range of 100 ° C. As the organic solvent, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and ethers are preferably used.

Next, in the reaction of the chiral compound of the above general formula [3] obtained by the above reaction with the compound of the above general formula [4], 2 equivalents of the compound of the general formula [3] The compound of the formula [4] is reacted with the compound of the general formula [5]
To a chiral compound. This reaction is carried out without solvent or in an organic solvent inert to the reaction, and the reaction temperature is-
It is performed in the range of 90 to 100 ° C. As the organic solvent, aliphatic hydrocarbons, aromatic hydrocarbons and ethers are preferable, and particularly, tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane is used.

As the alkali metal in the dialkali metal salt of the chiral compound of the above general formula [5] obtained by the above reaction, lithium, sodium or potassium is particularly preferably used. Compounds include, for example, organolithium compounds such as methyllithium and butyllithium, sodium metals such as sodium and sodium hydride or their hydrides, potassium metals such as potassium and potassium hydride or their hydrides, and aliphatic hydrocarbons. Contact with an organic solvent such as an aromatic hydrocarbon and an ether to form a compound of the general formula [5]
Can be obtained.

In the present invention, the general formula MXn (M) is reacted with a dialkali metal salt of a chiral compound of the general formula [5].
Is a metal selected from Group 4 of the periodic table, X is a halogen, and n is an integer of 3 or 4. ) Or the ether complex includes titanium tri- or tetrafluoride;
Chloride, bromide and iodide, zirconium tetrafluoride, chloride, bromide and iodide, and hafnium tetrafluoride, chloride, bromide and iodide or their tetrahydrofuran, diethyl ether, dioxane or 1,2- Complexes with ether compounds such as dimethoxyethane can be mentioned. In the reaction between the dialkali metal salt of the compound of the general formula [5] and the general formula MXn or the ether complex, the dialkali metal salt and the general formula MXn or the ether complex are equimolarly reacted in an organic solvent at a reaction temperature of Is performed in the range of -90 ° C to room temperature. As the organic solvent, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and ethers are used, and in particular, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane and the like are preferably used.

In the present invention, the metallocene compound represented by the above general formula [1] obtained by the above synthesis method is a chiral complex, and the meso form is not formed by the synthesis of the complex, and the racemate is selectively formed. Is obtained.

The chiral complex of the present invention preferably has the structure represented by the above general formula [1], and the α-olefin calculated by the molecular mechanics method is re-coordinated. -The difference in steric repulsion energies when coordinated is 4.0 kcal / mol or more. The calculation method using this molecular force field is performed using commercially available software. Specifically, molecular design support software: UNIVERSAL FOR built in Cerius2
This is performed using CE FIELD. Specific methods include, for example, a lecture by Tanaka (4th Forum of Precision Polymerization Forum, 2. Computer simulation of transition metal complex polymerization) and a report by Asanuma (Journal of the Rubber Association of Japan, No. 6).
9, 163 (1996)).

The specific examples of the above-mentioned metallocene compounds in the present invention are shown below, but are not particularly limited as long as they are optically active and chiral metallocene compounds as described above. (1R, 2R) or (1S, 2S)-
1,2-dimethylethylenediyl-1,2-bis (2 ′
-Methylindenyl) zirconium dichloride or
A mixture of the (1R, 2R) and (1S, 2S) complex, (1
R, 2R) or (1S, 2S) -1,2-diisoprop
Propylethylenediyl-1,2-bis (2'-methylyl
Ndenyl) zirconium dichloride or the (1R,
2R) and (1S, 2S) complex mixture, (1R, 2R)
Or (1S, 2S) -1,2-dimethylethylenediyl
1,2-bis (2'-methyl-4'-isopropyl
Indenyl) zirconium dichloride or (1)
R, 2R) and (1S, 2S) complex mixture, (1R, 2
R) or (1S, 2S) -1,2-dimethylethylene
Ndiyl-1,2-bis (2'-methyl-4'-cyclo
Hexylindenyl) zirconium dichloride or
A mixture of the (1R, 2R) and (1S, 2S) complex, (1
(R, 2R) or (1S, 2S) -1,2-dimethyl
Ethylenediyl-1,2-bis (2'-methyl-4'-
Phenylindenyl) zirconium dichloride or
A mixture of the (1R, 2R) and (1S, 2S) complex, (1
(R, 2R) or (1S, 2S) -1,2-dimethyl
Ethylenediyl-1,2-bis (2'-methyl-4'-
Naphthylindenyl) zirconium dichloride or
A mixture of the (1R, 2R) and (1S, 2S) complex, (1
(R, 2R) or (1S, 2S) -1,2-dimethyl
Ethylenediyl-1,2-bis (2'-methyl-4'-
Isopropoxyindenyl) zirconium dichloride
Or a mixture of the (1R, 2R) and (1S, 2S) complexes,
(1R, 2R) or (1S, 2S) -1,2-dimension
Butylethylenediyl-1,2-bis (2′-methylben
[E] indenyl) zirconium dichloride or
A mixture of the (1R, 2R) and (1S, 2S) complex, (1
(R, 2R) or (1S, 2S) -1,2-dimethyl
Ethylenediyl-1,2-bis (2′-methylbenz
[F] indenyl) zirconium dichloride or the same
(1R, 2R) and (1S, 2S) complex mixture, (1R,
2R) or (1S, 2S) -1,2-dimethylethyl
Rangeyl-1,2-bis (2'-methyl-4'-iso
Propylindenyl) zirconium dimethyl or
( 1R, 2R) and (1S, 2S) complex mixture, (1R, 2R)
2R) or (1S, 2S) -1,2-dimethylethyl
Rangeyl-1,2-bis (2'-methyl-4'-fe
Nylindenyl) zirconium dimethyl or the (1)
R, 2R) and (1S, 2S) complex mixture, (1R, 2
R) or (1S, 2S) -1,2-dimethylethylene
Ndiyl-1,2-bis (2'-methyl-4'-naphthyl)
Ruindenyl) zirconium dimethyl or the (1)
R, 2R) and (1S, 2S) complex mixture, (1R, 2
R) or (1S, 2S) -1,2-dimethylethyl
N-diyl-1,2-bis (2'-methylbenz [e] i
Ndenyl) zirconium dimethyl or the (1R, 2
R) and (1S, 2S) complex mixture, (1R, 2R)
Or (1S, 2S) -1,2-dimethylethylenediyl
-1,2-bis (2'-methyl-4'-isopropyli
Ndenyl) titanium dimethyl or the (1R, 2
R) and (1S, 2S) complex mixture, (1R, 2R)
Or (1S, 2S) -1,2-dimethylethylenediyl
-1,2-bis (2'-methyl-4'-phenylindene
Nyl) zirconium dimethyl or the (1R, 2R)
And (1S, 2S) complex mixture, (1R, 2R) or
(1S, 2S) -1,2-dimethylethylenediyl-
1,2-bis (2'-methyl-4'-naphthylindeni
Le) Titanium dimethyl or (1R, 2R)
(1S, 2S) complex mixture, (1R, 2R) or
(1S, 2S) -1,2-dimethylethylenediyl-
1,2-bis (2'-methylbenz [e] indenyl)
Titanium dichloride or (1R, 2R) and (1
(S, 2S) complex mixture, (1R, 3R) or (1R, 3R)
S, 3S) -1,3-dimethylpropylenediyl-1,
3-bis (2'-methyl-4'-isopropylindeni
C) hafnium dichloride or (1R, 3R) or
And (1S, 3S) complex mixture, (1R, 3R) or
(1S, 3S) -1,3-dimethylpropylenediyl-
1,3-bis (2'-methyl-4'-phenylindeni
Le) Hafnium dichloride or (1R, 3R)
(1S, 3S) complex mixture, (1R, 3R) or
(1S, 3S) -1,3-dimethylpropylenediyl-
1,3-bis (2'-methyl-4'-naphthylindeni
Le) Hafnium dichloride or (1R, 3R)
(1S, 3S) complex mixture, (1R, 3R) or
(1S, 3S) -1,3-dimethylpropylenediyl-
1,3-bis ( 2'-methylbenz [e] indenyl)
Hafnium dichloride or (1R, 3R) and (1
(S, 3S) complex mixture .

In the present invention, the olefin to be polymerized by using the above metallocene compound is an olefin having 2 to 20 carbon atoms.
Olefins (including ethylene), preferably 2 carbon atoms
To 10 to 10 α-olefins. Specific examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, styrene and the like. Further, butadiene, 1,4-pentadiene,
C4-C20 dienes such as 1,5-hexadiene and 1,4-hexadiene, or cyclic olefins such as dicyclopentadiene, norbornene, methylnorbornene, tetracyclododecene, and methyltetracyclododecene, or allyl And silicon-containing olefins such as trimethylsilane and vinyltrimethylsilane. In addition, these olefins can be polymerized alone,
Polymerization may be carried out in combinations of more than one kind.

In the present invention, the aluminoxane used in combination with the olefin polymerization using the above metallocene compound is represented by the following general formula [6]:

[0035]

Embedded image

Alternatively, a compound represented by the general formula [7] (Formula 12) is used.

[0037]

Embedded image Wherein R ¹¹ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or hydrogen, and p is an integer of 2 to 50, preferably 10 to 35. )

The ratio of the aluminoxane represented by the general formulas [6] and [7] to the metallocene compound is 1 to 1000 as aluminum / metallocene.
It is generally 0 mole times. When using the above aluminoxane, it is also possible to use an organic aluminum compound having 1 to 20 carbon atoms in combination, and in this case, good performance can be obtained with a relatively small amount of aluminoxane. Examples of such organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum,
sec-butylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, disec-butylaluminumchloride and the like.

In the present invention, when the olefin is polymerized using the above metallocene compound, the metallocene compound used in combination is converted into a cationic compound, and the ionic compound and the organoaluminum compound which generate stable counter anion species are: As the ionic compound, as a specific example,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, N, N-dimethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, Carbenium borane such as triethylammonium tetratetrakis (phenyl) borate and tri-n-butylammonium tetra (phenyl) borate, metalabran, ammonium borane and the like are mentioned, and for example, JP-A Nos. 1-501950 and 1-5202036. It is exemplified in a gazette or the like. Also,
The ratio of the ionic compound to the metallocene compound used is 0.1 as ionic compound / metallocene.
It is 1 to 10 mole times. As the organic aluminum compound, an organic aluminum compound having 1 to 20 carbon atoms is used in combination, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum,
Triisobutylaluminum, trisec-butylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride,
Examples thereof include diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and disec-butylaluminum chloride. The ratio of the organoaluminum compound to the metallocene compound is from 1 to 10,000 mol times as the organoaluminum compound / metallocene.

In the present invention, polymerization is carried out by a usual solvent polymerization method.
Besides, it is also possible to carry out by bulk polymerization method or gas phase polymerization method.
The polymerization temperature is usually -100 to 200C, preferably
Or -20 to 100 ° C. Especially as polymerization pressure
No restriction, normal pressure ~ 50kgf / cm ^TwoIt is.

[0041]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

In the present invention, optical purity (ee), molecular weight distribution index (PDI), intrinsic viscosity ([η]) and tacticity (mmmm) of the polymer were measured by the following methods. -Optical purity (ee): ee = [(R, R)-(S, S)] x100 / [(R, R) + (S,
S)]; Analysis by gas chromatography under the following conditions was calculated by the area integration method. Measuring device: Shimadzu GC-
9A, column: Chromopack CP-Cyclodextrin-β-2,3,6
-M-19 Columm (L = 50m, ID = 0.25 mm), Column temperature: 1
10 ° C., injection temperature: 250 ° C., carrier gas: nitrogen Molecular weight distribution index (PDI): PDI = Mw / Mn; number average molecular weight (Mn) and weight average molecular weight (Mw) are measured by gel permission chromatography under the following conditions: did. Measuring device: Waters 150CVplus, Column: Shodex G
PC AD-80M / S (exclusion limit: 2 × 10 ⁷ ), mobile phase: trichlorobenzene, column temperature: 135 ° C., measurement flow rate: 1.0 ml
/ min., sample concentration: 0.2 wt / vol%, injector volume: 0.200 ml, detector: differential refractometer and viscometer,
Standard sample: polystyrene standard Intrinsic viscosity ([η]): The viscosity is measured in tetralin at 135 ° C. and expressed in dl / g. Stereoregularity of polymer (mmm
m): Pentad fraction measuring device showing stereoregularity based on polymer side chain methyl group by ¹³ C-NMR spectrum: JEOL JNM-EX270, solvent: mixed solution of trichlorobenzene / deuterated benzene, measurement temperature:
125 ° C, sample concentration: 100mg / ml

Example 1 [Synthesis of (1R, 2R) -1,2-dimethylethylenediylbis (2'-methylbenz [e] indenyl) zirconium dichloride] (1) (2R, 3R) -2,3-butyldichloride (Triflate) Trifluoromethanesulfonic anhydride (18.80 g, 67 mm
ol) was converted to (2R, 3R) -2,3-butanediol (ee = 9).
9.0%) (3.00 g, 33 mmol) and pyridine (5.25 g, 66 mm)
ol) in dichloromethane (100 ml) under ice-cooling,
Stir for 1 hour. Further, water is added, the organic phase is separated,
After drying over anhydrous magnesium sulfate, the product obtained with hexane was passed through a silica gel column, concentrated and distilled to obtain a colorless liquid (5.31 g, 43 ° C./3 mmHg). The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ , TMS standard)
δ; 5.06 (dq, 2H), 1.61 (d, 6H) GC; Retention Tim
e = 24.6 min .: (R, R) form, 27.3 min .: (S, S) form; ee = 99%

(2) (2R, 3R) -2,3-bis (2
-Methylbenz [e] indenyl) butane Under a nitrogen atmosphere, (2-methylbenz [e] indenyl)
To a solution of lithium (4.2 g, 22.5 mmol) in tetrahydrofuran (hereinafter abbreviated as THF) (50 ml) was added (2R, 3
R) -2,3-Butyldi (triflate) (3.46 g, 9.
(8 mmol) in THF (10 ml) was added dropwise at -78 ° C, and the mixture was stirred at room temperature for 24 hours. A saturated aqueous ammonium chloride solution was added, the organic phase was separated, dried over anhydrous magnesium sulfate, and concentrated to give an orange color. Oil was obtained. This is then passed through a silica gel column with hexane / ethyl acetate,
The solvent was removed to give a yellow solid. Further, recrystallization from benzene gave colorless crystals (0.50 g). The analytical values are shown below. ¹ H-NMR (90 MHz, CDCl ₃ , TMS standard) δ; 7.71-7.
85 (m, 8H), 7.24-7.45 (m, 4H), 3.59 (q, 2H), 3.2
6 (d, 4H), 1.59 (d, 6H), 1.58 (s, 6H) Elemental analysis; Calculated C: 92.71, H: 7.29, Analytical value C: 92.64, H: 7.35

(3) (1R, 2R) -1,2-dimethylethylenediyl-1,2-bis (2'-methylbenz [e] indenyl) zirconium dichloride Obtained by the above method under a nitrogen atmosphere. 3R) -2,
A solution of 3-bis (2-methylbenz [e] indenyl) butane (310 mg, 0.74 mmol) in THF (20 ml) was added to an excess of potassium hydride (95 mg, 2.4 mmol) in THF (30 ml).
The suspension was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 24 hours, and then the suspension was filtered through celite. This filtrate was added dropwise to a suspension of zirconium tetrachloride (280 mg, 0.74 mmol) in THF (30 ml) at room temperature, and the mixture was stirred at room temperature for 24 hours. After removing the solvent, the obtained yellow solid was subjected to Soxhlet extraction with toluene, and the toluene was concentrated to obtain a yellow solid (200 mg).
The analytical values are shown below. ¹ H-NMR (90 MHz, CDCl ₃ , TMS standard) δ; 7.67-7.
86 (m, 4H), 7.35-7.58 (m, 6H), 7.00-7.29 (m 4
H), 3.48 (q, 2H), 1.26 (s, 6H), 1.24 (d, 6H) Elemental analysis; Calculated C: 66.88, H: 4.91, Analytical value C: 66.97,
H: 4.98

Example 2 [Calculation of steric repulsion energy] The structure in which propylene is coordinated with the metallocene compound synthesized in Example 1 was analyzed using UNI built in Cerius2, a molecular design support software.
Optimized using the parameters of VERAL FORCE FIELD. When the model of the polymer chain bonded to the central metal of the metallocene compound is an isobutyl group, the case where propylene is re-coordinated to the metallocene compound and the case where si-
The steric repulsion energy difference in the case of coordination was estimated. r
The difference in steric repulsion energies between e-coordinated and si-coordinated was 4.27 kcal / mol.

Example 3 [Polymerization of Propylene] Into a 2-liter autoclave sufficiently purged with nitrogen, 1 liter of dry toluene was charged, and after purging with propylene, 8.8 mmol of methylaluminoxane in terms of aluminum (manufactured by Tosoh Agzo Co., Ltd.) After charging propylene to 3 kg-G / cm ² -G at 20 ° C.,
A toluene solution of 2.5 mg (0.00435 mmol) of the yellow solid obtained in Example 1 was injected with propylene and polymerized at a constant pressure at 20 ° C. for 1 hour. After the polymerization, propylene was degassed, the solvent was removed by filtration, washed with heptane, and then dried under vacuum.
C. and dried for 6 hours. The obtained polymer is 142 g,
Polymerization activity was 32640 kg / mol Zr, [η] = 3.17 dl / g, Mw
= 792000, PDI = 1.90, mmmm = 0.973.

Comparative Example 1 In the same manner as in Example 1 except that the metallocene compound was 1,2-ethylenebis (indenyl) zirconium dichloride, the case where propylene was re-coordinated and the case where propylene was si-coordinated to the metallocene compound The steric repulsion energy difference was estimated. The steric repulsion energy difference between the case of re-coordination and the case of si-coordination is 3.92 kcal / mo.
l.

A 1-liter autoclave sufficiently purged with nitrogen was charged with 500 ml of dry toluene, and then purged with propylene.
mmol of methylaluminoxane (Tosoh Agzo Co., Ltd.)
Propylene), and propylene at 20 ° C. to 5 kg / cm ² -G, followed by 1,2-ethylenebis (indenyl)
0.11 mg of zirconium dichloride (0.00026
mmol) of toluene solution, and pressurized at constant pressure.
Polymerization was performed at 26 ° C. for 2 hours. After the polymerization, propylene was degassed, the solvent was removed by filtration, washed with heptane, and dried under vacuum at 80 ° C. for 6 hours. The obtained polymer was 34.8 g, and [η] = 0.67 dl / g, mm
mm = 0.804, Tm = 135 ° C., Tc = 100 ° C.

[0051]

By carrying out the process of the present invention, it is possible to produce a highly stereoregular polymer of olefin with high yield, which is extremely valuable industrially.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-106907 (JP, A) JP-A-6-184179 (JP, A) JP-A-4-227708 (JP, A) JP-A-5-207 140227 (JP, A) JP-A-5-306304 (JP, A) JP-A-6-157662 (JP, A) JP-A-1-501950 (JP, A) JP-A-1-502036 (JP, A) European Patent Application Publication 545303 (EP, A1) European Patent Application Publication 645401 (EP, A1) Chem. Pp. 499-503 Organometallics 1992, 11, pp. 1869-1876 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 17/00 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. A novel chiral metallocene compound represented by the following general formula [1]. Embedded image ( Wherein C ¹ and C ² represent asymmetric carbons, and R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, and have 1 to 20 carbon atoms.
Linear alkyl group, branched alkyl having 3 to 20 carbon atoms
Group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, a linear alkoxy group having 1 to 20 carbon atoms,
A branched alkoxy group having 3 to 20 carbon atoms, 3 to 20 carbon atoms
Cyclic alkoxy group, aryloxy having 6 to 20 carbon atoms
Group, a silicon-containing alkyl group, and R ¹⁰ has 1 carbon atom.
-20 linear alkyl group, branched alkyl group having 3-20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
Alkoxy group, selected from a silicon-containing alkyl group, also, R ¹
And R ² and R ³ and R ⁴ are different from each other, and the asymmetric carbon C ¹ and C ²
Is represented by R, S notation (R, R) or (S,
S) or a mixture of (R, R) and (S, S).
R ^{5 to} R ⁹ may be such that R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are directly bonded to each other to form the same cyclic hydrocarbon substituent; M is a metal selected from Group 4 of the periodic table, Y is bonded to C ¹ and C ² atoms, and methylene,
Dimethylmethylene, diphenylmethylene, dimethylsilicone
X is selected from the group consisting of
Is selected from a halogen, an alkyl group or an anionic ligand, n is 0 or 1, and m is an integer of 1 or 2. ) 2. A chiral compound represented by the following general formula [2] (Formula 2) is reacted with a trihalomethanesulfonic acid derivative to obtain a chiral compound represented by the following general formula [3] (Formula 3):
Further, the compound is reacted with a compound represented by the following general formula [4] (formula 4) to obtain a chiral compound represented by the following general formula [5] (formula 5). Then, a dialkali metal salt of the compound is converted into a general formula MXn (M is a periodic table). A metal selected from Group 4; X is a halogen; n is an integer of 3 or 4); or reacting with the ether complex of MXn . A method for synthesizing a novel chiral metallocene compound. Embedded image (Wherein, C ¹ and C ² represent an asymmetric carbon; R ¹ , R ² , R ³ and R ⁴ represent hydrogen, a linear alkyl group having 1 to 20 carbon atoms,
A branched alkyl group having a prime number of 3 to 20, a ring having a carbon number of 3 to 20
Alkyl group, aryl group having 6 to 20 carbon atoms, 1 carbon atom
To 20 linear alkoxy groups, 3 to 20 carbon atoms, branched
Alkoxy group, cyclic alkoxy group having 3 to 20 carbon atoms, carbon
An aryloxy group prime 6-20, selected from a silicon-containing alkyl group, also, R ¹ and R ² and R ³ and R ⁴ are different from each other, the configuration of the asymmetric carbon C ¹ and C ² is, R, S Notation is (R, R) or (S, S), or a mixture of (R, R) and (S, S), OH represents a hydroxy group, Y is bonded to C ¹ and C ² atoms, Methylene, dimethi
Lmethylene, diphenylmethylene, dimethylsilylene,
It is selected from diphenylsilylene, and n is 0 or 1. ) (Wherein, C ¹ and C ² represent an asymmetric carbon; R ¹ , R ² , R ³ and R ⁴ represent hydrogen, a linear alkyl group having 1 to 20 carbon atoms,
A branched alkyl group having a prime number of 3 to 20, a ring having a carbon number of 3 to 20
Alkyl group, aryl group having 6 to 20 carbon atoms, 1 carbon atom
To 20 linear alkoxy groups, 3 to 20 carbon atoms, branched
Alkoxy group, cyclic alkoxy group having 3 to 20 carbon atoms, carbon
An aryloxy group prime 6-20, selected from a silicon-containing alkyl group, also, R ¹ and R ² and R ³ and R ⁴ are different from each other, the configuration of the asymmetric carbon C ¹ and C ² is, R, S Notation is (R, R) or (S, S) or a mixture of (R, R) and (S, S), L is a trihalomethanesulfonyl group, Y is bonded to C ¹ and C ² atoms , Metile
Dimethyl methylene, diphenyl methylene, dimethyl
Selected from silylene and diphenylsilylene
And n is 0 or 1. ) ( Wherein , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, having 1 to 1 carbon atoms)
20 straight-chain alkyl groups, branched alkyl groups having 3 to 20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
R ¹⁰ is selected from a xy group and a silicon-containing alkyl group,
Number 1 to 20 linear alkyl group, C 3 to C 20 branched
Alkyl group, cyclic alkyl group having 3 to 20 carbon atoms, carbon number
6-20 aryl groups, linear alcohols having 1-20 carbon atoms
Xy group, branched alkoxy group having 3 to 20 carbon atoms, carbon number
Cyclic alkoxy group having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms
Roxy group, selected from silicon-containing alkyl group, R ¹⁰ is
1 to 20 carbon atoms linear alkyl group, 3 to 20 carbon atoms
Cyclic alkyl group, cyclic alkyl group having 3 to 20 carbon atoms, carbon
An aryl group having 6 to 20 primes, a linear a
Alkoxy group, branched alkoxy group having 3 to 20 carbon atoms, carbon
A cyclic alkoxy group having a prime number of 3 to 20;
Selected from a reeloxy group and a silicon-containing alkyl group , and R ^{5 to} R ⁹ are R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R
⁸ and R ⁹ may be directly bonded to each other to form the same cyclic hydrocarbon substituent, and K is selected from alkali metals. ) ( Wherein C ¹ and C ² represent asymmetric carbons, and R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen, and have 1 to 20 carbon atoms.
Linear alkyl group, branched alkyl having 3 to 20 carbon atoms
Group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, a linear alkoxy group having 1 to 20 carbon atoms,
A branched alkoxy group having 3 to 20 carbon atoms, 3 to 20 carbon atoms
Cyclic alkoxy group, aryloxy having 6 to 20 carbon atoms
Group, a silicon-containing alkyl group, and R ¹⁰ has 1 carbon atom.
-20 linear alkyl group, branched alkyl group having 3-20 carbon atoms
Kill group, cyclic alkyl group having 3 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryl groups, linear alkoxy having 1 to 20 carbon atoms
Group, C3-20 branched alkoxy group, C3-3
20 cyclic alkoxy groups, arylo having 6 to 20 carbon atoms
Alkoxy group, selected from a silicon-containing alkyl group, also, R ¹
And R ² and R ³ and R ⁴ are different from each other, and the asymmetric carbon C ¹ and C ²
Is represented by R, S notation (R, R) or (S,
S) or a mixture of (R, R) and (S, S).
R ^{5 to} R ⁹ may be such that R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are directly bonded to each other to form the same cyclic hydrocarbon substituent; Y is bonded to C ¹ and C ² atoms,
Methylene, dimethylmethylene, diphenylmethylene, di
Selected from methylsilylene and diphenylsilylene
And n is 0 or 1. ) 3. A metallocene compound represented by the general formula [1], wherein the α-olefin calculated by a molecular mechanics method is r
A novel metallocene compound characterized in that the difference in steric repulsion energies between e-coordinated and si-coordinated is 4.0 kcal / mol or more. 4. A method for polymerizing an olefin, comprising polymerizing an olefin using a metallocene compound represented by the general formula [1]. 5. The method according to claim 4, wherein the metallocene compound represented by the general formula [1] is used in combination with an aluminoxane. 6. A metallocene compound represented by the general formula [1] and a carbenium borane, metalaborane, which converts the compound into a cationic compound to generate a stable counter anion species .
The method according to claim 4 , wherein an organic aluminum compound is used in combination with an ionic compound selected from ammonium borane . 7. R ¹ , R ⁴ and R ¹⁰ are methyl, R ² , R ³ and R ⁹
Is hydrogen, M is zirconium, X is chlorine, n is 0, m is 2
Wherein R ⁵ and R ⁶ form the same ring and R ⁷ and R ⁸ are hydrogen, or R ⁵ and R ⁶ are hydrogen and R ⁷ and R ⁸ form the same ring The metallocene compound according to claim 1, which is benz. 8. The method according to claim 4, wherein the metallocene compound according to claim 7 is used in combination with an aluminoxane. 9. Convert the claims metallocene compound of claim 7, wherein the said compound in the cationic compound generating a stable pair anionic species, carbenium boranes, Metaraboran, A Nmoni
The method according to claim 4, wherein an ionic compound selected from umborane and an organoaluminum compound are used in combination.