JP2004161760A - New transition metal compound, olefin polymerization catalyst and method for producing polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new transition metal compound having high activity as a component of an olefin polymerization catalyst, while containing no halogen element. <P>SOLUTION: This transition metal compound is composed of a transition metal of the group IV in the periodic table and ligands comprising three cyclopentadienyl ligands and one hydrogen atom, wherein at least one of the cyclopentadienyl ligands is a substituted cyclopentadienyl. The olefin polymerization catalyst comprises the transition metal compound and an organic aluminumoxy compound and/or a compound which reacts with the transition metal compound to form an ion pair. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a novel transition metal compound, a catalyst for olefin polymerization, and a method for producing a polyolefin.

A number of compounds having a transition metal compound of Group 4 of the periodic table as a central metal and having a cyclopentadienyl ligand or a substituted cyclopentadienyl ligand as a ligand have been synthesized and used in organic synthesis reactions. For example, it is well known that it is widely used as a polymerization catalyst (for example, SYNTHESIS, January 1988, 1-19, JP-A-58-19309, etc.). Further, it is said that the introduction of a substituent into the cyclopentadienyl ligand changes the molecular weight and density of the polymer in olefin copolymerization (Japanese Patent Publication No. 7-37488).
However, most of these transition metal compounds are monocyclopentadienyl compounds, monosubstituted cyclopentadienyl compounds or biscyclopentadienyl compounds, bis-substituted cyclopentadienyl compounds.
Here, several triscyclopentadienyl compounds and tris-substituted cyclopentadienyl compounds have been reported. For example, Cp ₃ ZrCl (Bul. Chem. Soc. Fr., 1978, II-292), Cp ₃ ZrMe (Organometallics 1997, 16, 531), (MeCp) ₃ ZrCl (Bul. Chem. Soc. Fr., 1978) , II-292), (Me ₃ SiCp) ₃ ZrCl (Acta. Cryst., 1995, C51, 10), Ind ₃ MCl (M = Zr, Hf) (J. Organomet. Chem., 1997, 544, 139). And so on, but the number is small.
Furthermore, as for the triscyclopentadienyl metal hydride compound and the tris-substituted cyclopentadienyl metal hydride compound (metal is a Group 4 transition metal), only Cp ₃ ZrH has been reported so far (IR analysis and Raman The structural analysis by the analytical method is described in J. Organomet. Chem., 1982, 235, 69, and the structural analysis by the X-ray diffraction method is described in Organometallics, 1999, 18, 3170). The method for synthesizing compounds, only a method of reacting t-BuLi to a method and _Cp 4 Zr reacting LiAlH ₄ to _Cp 4 Zr is known. Other than these synthesis methods, a method of reacting Cp ₃ ZrCl with LiAlH ₄ and a method of reacting Cp ₃ ZrCl with alkyl lithium are conceivable. However, in these methods, side reactions such as removal of the Cp ligand occur, and it is difficult to obtain a target product. In addition, there have been few reports of tetrakiscyclopentadienyl zirconium compounds containing at least one substituted cyclopentadienyl group other than Cp, possibly due to a large steric repulsion.
That is, a transition metal compound in which at least one of the three cyclopentadienyl ligands is a substituted cyclopentadienyl group has not been known at all.
JP-A-58-19309 Japanese Patent Publication No. 7-37488 SYNTHESIS, January 1988, 1-19 Bull. Chem. Soc. Fr. , 1978, II-292. Organometallics 1997, 16, 531 Acta. Cryst. , 1995, C51 10 J. Organomet. Chem. , 1997, 544, 139. J. Organomet. Chem. , 1982, 235, 69 Organometallics, 1999, 18, 3170

Usually, a monocyclopentadienyl metal compound, a biscyclopentadienyl metal compound, and a triscyclopentadienyl metal compound are stably present as halides such as chlorides (metals are transition metals of Group 4 of the periodic table). A small amount of a halogen compound originating from the catalyst exists in the polyolefin polymerized using these. Even though the amount is small, polyolefin containing a halogen compound is easily oxidized by heat or light and may be discolored to yellow or the like. Therefore, an additive such as an antioxidant or a halogen catcher is often added to the polyolefin.
However, in recent years, awareness of environmental problems has increased, and polyolefins containing no additives such as halides and antioxidants, which are considered to have an adverse effect on the human body, have been demanded. Particularly in the food packaging field and the medical field, there is a strong demand for halogen-free and additive-free polyolefins. Examples of the metal compound containing no halogen element (the metal is a transition metal of Group 4 of the periodic table) include a monocyclopentadienyl metal alkyl compound and a biscyclopentadienyl metal alkyl compound, and these are the respective halides. Can be prepared using a Grignard reagent or alkyl lithium.
However, most of the compounds having hydrogen at the β-position among them do not stably exist due to a β-hydrogen elimination reaction or the like. Compounds having no hydrogen at the β-position, such as methylated and benzylated compounds, can exist as thermodynamically stable compounds without β-hydrogen elimination reaction. However, these alkyl compounds easily react and decompose when a trace amount of water, oxygen, or the like is present in the system, and therefore must be strictly stored in an inert gas atmosphere. In addition, in order to synthesize an alkyl compound from triscyclopentadienyl metal halide, a general method for synthesizing a complex using a Grignard reagent or alkyllithium is a method generally used to synthesize three cyclopentadienyl ligands. A reaction such as the removal of one occurs, and it is difficult to synthesize an alkyl compound with high yield by this method.

The present invention provides a novel transition metal compound that has not been known so far. This novel transition metal compound becomes a catalyst component having excellent polymerization activity when used for polymerizing an olefin. Also, since the novel transition metal compound does not contain a halogen element, the halogen element is not contained in the polyolefin which is a polymer, so that the amount of the additive to be added can be reduced as compared with the conventional one, or Can be used without addition. These novel transition metal compounds are novel transition metal compounds comprising a Group 4 transition metal, ligands of three cyclopentadienyl derivatives and hydrogen, and such transition metal compounds have not been known so far. . Further, it has not been known at all that the transition metal compound is used as a catalyst component for olefin polymerization.
The novel transition metal compound of the present invention is a transition metal compound having no halogen element and having three cyclopentadienyl derivatives and one hydrogen atom as a ligand. By comparison, it is relatively stable to water and oxygen.

  The present invention provides a novel transition metal compound having high activity as a catalyst component for olefin polymerization and containing no halogen element, wherein at least one of three cyclopentadienyl ligands has a substituted cyclopentadienyl group. Which is a transition metal compound of Group 4 of the periodic table having a ligand consisting of a hydrogen atom.

  The present invention provides a novel transition metal compound that has not been known hitherto. The transition metal compound becomes an olefin polymerization catalyst component having excellent polymerization activity. Further, since the transition metal compound does not include a halogen element, the halogen element is not included in the olefin polymer, and therefore, the amount of the stabilizer and the like can be reduced.

Hereinafter, the present invention will be described in detail.
The first novel transition metal compound of the present invention is represented by the following general formula (1).
_{^{(C 5 R 1 R 2 R}} 3 R 4 R 5) (C 5 R 6 R 7 R 8 R 9 R 10) (C 5 R 11 R 12 R 13 R 14 R 15) M 1 H ··· formula ( 1)
_{^{Wherein, (C 5 R 1 R 2}} R 3 R 4 R 5), (C 5 R 6 R 7 R 8 R 9 R 10) and _{^{(C 5 R 11 R 12 R}} 13 R 14 R 15) , respectively Represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and represents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. Good. Among them, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). However, at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ Is a substituent other than a hydrogen atom. M ¹ represents a transition metal of Group 4 of the periodic table. ]

The second transition metal compound of the present invention is represented by the following general formula (2).
_{^{(C 5 R 16 R 17 R}} 18 R 19 R 20) (C 5 R 21 R 22 R 23 R 24 R 25) (C 5 H 2 R 26 R 27 R 28) M 2 H ··· formula (2)
[Wherein C ₅ R ¹⁶ R ¹⁷ R ¹⁸ R ¹⁹ R ²⁰ , C ₅ R ²¹ R ²² R ²³ R ²⁴ R ²⁵ , and C ₅ H ₂ R ²⁶ R ²⁷ R ²⁸ each represent a cyclopentadienyl group, or Represents a substituted cyclopentadienyl group, and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are hydrogen. An atom, a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, which may be the same or different. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , or R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , or R ²⁶ , R ²⁷ , R ²⁸ are respectively bonded to each other to form a ring. A hydrocarbon group (including a polycyclic structure) may be formed. However, at least one of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ is a substitution other than a hydrogen atom. Group. M ² represents a periodic table group IV transition metals. ]

The third transition metal compound of the present invention is represented by the above general formula (2), wherein R ²⁶ , R ²⁷ , and R ²⁸ are bonded to adjacent carbons at the first, second, and third positions. It is.

The fourth transition metal compound of the present invention is represented by the following general formula (3).
_{^{(C 5 H 2 R 29 R}} 30 R 31) (C 5 H 2 R 32 R 33 R 34) (C 5 H 2 R 35 R 36 R 37) M 3 H
... Equation (3)
[Wherein (C ₅ H ₂ R ²⁹ R ³⁰ R ³¹ ), (C ₅ H ₂ R ³² R ³³ R ³⁴ ), and (C ₅ H ₂ R ³⁵ R ³⁶ R ³⁷ ) each represent cyclopentadienyl. R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ represent a hydrogen atom, a carbon atom having 1 to 30 carbon atoms, or a substituted cyclopentadienyl group. An organic silicon group having a hydrogen group or a hydrocarbon having 1 to 30 carbon atoms as a substituent, and may be the same or different. In addition, R ²⁹ , R ³⁰ , R ³¹ , or R ³² , R ³³ , R ³⁴ , or R ³⁵ , R ³⁶ , R ³⁷ are bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). It may be formed. However, at least one of R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ is a substituent other than a hydrogen atom. M ³ represents a transition metal of Group 4 of the periodic table. ]

The fifth transition metal compound of the present invention is represented by the above general formula (3), and R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , or R ³⁵ , R ³⁶ , R ^37. Is a transition metal compound bonded to adjacent carbons at the 1-, 2-, and 3-positions.

The sixth transition metal compound of the present invention is represented by the above general formula (3) and has three substituted cyclopentadienyl groups, (C ₅ H ₂ R ²⁹ R ³⁰ R ³¹ ) and (C ₅ H ₂ R). ³² R ³³ R ³⁴ ) and (C ₅ H ₂ R ³⁵ R ³⁶ R ³⁷ ) are transition metal compounds having the same structure.

The seventh transition metal compound of the present invention is represented by the following general formula (4).
_{^{(C 5 H 3 R 38 R}} 39) (C 5 H 3 R 40 R 41) (C 5 H 3 R 42 R 43) M 4 H
... Equation (4)
[Wherein (C ₅ H ₃ R ³⁸ R ³⁹ ), (C ₅ H ₃ R ⁴⁰ R ⁴¹ ), and (C ₅ H ₃ R ⁴² R ⁴³ ) each represent a cyclopentadienyl group or a substituted cycloalkyl group; Represents a pentadienyl group, and R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms as a substituent; Organosilicon groups which may be the same or different. Further, R ³⁸ and R ³⁹ , or R ⁴⁰ and R ⁴¹ , or R ⁴² and R ⁴³ may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). However, at least one of R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ is a substituent other than a hydrogen atom. M ⁴ represents a transition metal of Group ⁴ of the periodic table. ]

The eighth transition metal compound of the present invention is represented by the above general formula (4) and has three substituted cyclopentadienyl groups, (C ₅ H ₃ R ³⁸ R ³⁹ ) and (C ₅ H ₃ R ⁴⁰ R). ⁴¹ ) and (C ₅ H ₃ R ⁴² R ⁴³ ) are transition metal compounds having the same structure.

The ninth transition metal compound of the present invention is represented by the following general formula (5).
_{^{(C 9 R 44 R 45 R}} 46 R 47 R 48 R 49 R 50) (C 9 R 51 R 52 R 53 R 54 R 55 R 56 R 57) (C 9 R 58 R 59 R 60 R 61 R 62 R ⁶³ R ^{64) M} 5 H ··· formula (5)
[Wherein (C ₉ R ⁴⁴ R ⁴⁵ R ⁴⁶ R ⁴⁷ R ⁴⁸ R ⁴⁹ R ⁵⁰ ), (C ₉ R ⁵¹ R ⁵² R ⁵³ R ⁵⁴ R ⁵⁵ R ⁵⁶ R ⁵⁷ ) and (C ₉ R ⁵⁸ R ⁵⁹⁾ R ⁶⁰ R ⁶¹ R ⁶² R ⁶³ R ⁶⁴ ) each represents an indenyl group or a substituted indenyl group, and R ^{44 to} R ⁶⁴ represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a carbon group having 1 to 30 carbon atoms. These are organosilicon groups having hydrogen as a substituent, and may be the same or different. Further, among these ^R 44 ^{to R 50} or ^R 51 ^{to R 57,} or ^R 58 ^{to R 64} may be combined with each other to form a cyclic hydrocarbon group (including polycyclic structure). M ⁵ represents a periodic table group IV transition metals. ]

The tenth transition metal compound of the present invention is represented by the following general formula (6).
_{^{(C 9 H 3 R 65 R}} 66 R 67 R 68) (C 9 H 3 R 69 R 70 R 71 R 72) (C 9 H 3 R 73 R 74 R 75 R 76) M 6 H ··· formula ( 6)
[Wherein (C ₉ H ₃ R ⁶⁵ R ⁶⁶ R ⁶⁷ R ⁶⁸ ), (C ₉ H ₃ R ⁶⁹ R ⁷⁰ R ⁷¹ R ⁷² ) and (C ₉ H ₃ R ⁷³ R ⁷⁴ R ⁷⁵ R ⁷⁶ ) are each Represents an indenyl group or a substituted indenyl group, and R ^{65 to} R ⁷⁶ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent; They may be the same or different. Among them, R ^{65 to} R ⁶⁸ , R ^{69 to} R ⁷² , and R ^{73 to} R ⁷⁶ are bonded to the 4-, 5-, 6-, and 7-positions (6-membered ring portions) of the respective indenyl groups. May be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). M ⁶ represents a transition metal of Group 4 of the periodic table. ]

The eleventh transition metal compound of the present invention is represented by the above general formula (6) and has three substituted indenyl groups: (C ₉ H ₃ R ⁶⁵ R ⁶⁶ R ⁶⁷ R ⁶⁸ ) and (C ₉ H ₃ R ^69). R ⁷⁰ R ⁷¹ R ⁷² ) and (C ₉ H ₃ R ⁷³ R ⁷⁴ R ⁷⁵ R ⁷⁶ ) are transition metal compounds having the same structure.

  The twelfth transition metal compound of the present invention is a transition metal compound in which the transition metal of Group 4 of the periodic table in the above general formulas (1) to (6) is Zr.

  The olefin polymerization catalyst of the present invention is an olefin comprising the transition metal compound according to any one of the above first to twelfth, and an organoaluminum oxy compound and / or a compound that reacts with the transition metal compound to form an ion pair. It is a polymerization catalyst.

  The second olefin polymerization catalyst of the present invention is the olefin polymerization catalyst described above, wherein the organoaluminum oxy compound is methylaluminoxane.

  The third olefin polymerization catalyst of the present invention is an olefin polymerization catalyst, which is a solid catalyst in which the above catalyst is supported on a carrier.

  The fourth catalyst for olefin polymerization of the present invention is a solid catalyst in which the transition metal compound according to any one of the first to twelfth is supported on a layered silicate.

  The method for producing a polyolefin of the present invention is a method for producing a polyolefin, which comprises polymerizing an olefin in the presence of any of the olefin polymerization catalysts described above.

  The second method for producing a polyolefin of the present invention is a method for producing a polyolefin wherein the polymerization of the olefin is homopolymerization of ethylene or copolymerization of ethylene and an α-olefin.

Hereinafter, the transition metal compound of the present invention will be described in detail.
In the transition metal compounds of the present invention (general formula ^{_{(1)), C 5 R}} 1 R 2 R 3 R 4 R 5, C 5 R 6 R 7 R 8 R 9 R 10 and _{^{C 5 R 11 R 12 R 13}} R ¹⁴ R ¹⁵ represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent. Although they may be the same or different, they preferably have 1 to 24 carbon atoms, and more preferably 1 to 18 carbon atoms. Among them, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). However, at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ Is a substituent other than a hydrogen atom.
Examples of the hydrocarbon group of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl Group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group and other aryl groups; trityl group, phenethyl group, styryl group, benzhydryl group, phenylpropyl Groups, phenylbutyl groups, arylalkyl groups such as neophyl groups, etc. These may have branches.
Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a vinyl group, an allyl group, and a phenyl group. Among these compounds, a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group are particularly preferred.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ have 1 to 30 carbon atoms. Examples of the organosilicon group having a hydrocarbon as a substituent include an alkylsilyl group having an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group as a substituent; a vinyl group, Alkenylsilyl group having an alkenyl group such as an allyl group as a substituent; phenyl, dimethylphenyl, diethylphenyl, dipropylphenyl, dibutylphenyl, trimethylphenyl, triethylphenyl, tripropylphenyl, tributylphenyl An arylsilyl group having an aryl group such as a group, a biphenyl group, a naphthyl group, an anthryl group as a substituent; a trityl group, Enechiru group, styryl group, benzhydryl group, phenylpropyl group, phenylbutyl group, an aryl alkyl silyl group having an arylalkyl group in a substituent such as neophyl group. These may have branches.
Specific examples include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a trivinylsilyl group, a triallylsilyl group, and a triphenylsilyl group. Among these compounds, a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group are particularly preferred.
Among them, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ may form a cyclic hydrocarbon group (including a polycyclic structure) by bonding together, particularly adjacent groups.
_{^{C 5 R 1 R 2 R 3}} R 4 R 5 as a bond to form a cyclic hydrocarbon group (including polycyclic structure) to one _{^{another, C 5 R 6 R 7 R}} 8 R 9 R 10, C 5 R Specific examples of ¹¹ R ¹² R ¹³ R ¹⁴ R ¹⁵ include indenyl; alkyl indenyl having at least one alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; Alkenylindenyl having at least one alkenyl group such as vinyl group and allyl group; phenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group Having at least one aryl group such as tributylphenyl group, biphenyl group, naphthyl group, anthryl group, etc. Arylalkylindenyl having at least one arylalkyl group such as a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylpropyl group, a phenylbutyl group, a neophyl group; a tetrahydroindenyl; a polycyclic structure (Wherein benzoindenyl is a group having any structure represented by the following structural formula (Chemical Formula 1) or (Chemical Formula 2); the same applies hereinafter); a methyl group, an ethyl group, An alkylbenzoindenyl having at least one alkyl group such as a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; an alkenylbenzoindenyl having at least one alkenyl group such as a vinyl group and an allyl group; Dimethylphenyl, diethylphenyl, dipropylphenyl, diphenyl Arylbenzoindenyl having at least one aryl group such as butylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, styryl Alkyl benzoindenyl having at least one arylalkyl group such as a benzoyl group, a benzhydryl group, a phenylpropyl group, a phenylbutyl group, or a neophyl group; dibenzoindenyl having a polycyclic structure (dibenzoindenyl has the following structure An alkyldibenzoindenyl having one or more alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; ; Vinyl and allyl groups An alkenyl benzoindenyl having at least one alkenyl group of the formula: phenyl, dimethylphenyl, diethylphenyl, dipropylphenyl, dibutylphenyl, trimethylphenyl, triethylphenyl, tripropylphenyl, tributylphenyl, Aryldibenzoindenyl having at least one aryl group such as biphenyl group, naphthyl group and anthryl group; arylalkyl group such as trityl group, phenethyl group, styryl group, benzhydryl group, phenylpropyl group, phenylbutyl group, neophyl group, etc. Aryl alkyl dibenzoindenyl having one or more; azulenyl; alkyl azulenyl having at least one alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group. An alkenyl azulenyl having at least one alkenyl group such as a vinyl group or an allyl group; phenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl Azulenyl having at least one aryl group such as a group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, styryl group, benzhydryl group, phenylpropyl group, phenylbutyl group, neophyl group, etc. And arylalkylazulenyl having at least one arylalkyl group. Further, these substituents may have a branch.

More specific examples include indenyl, methylindenyl, ethylindenyl, propylindenyl, butylindenyl, vinylindenyl, allylindenyl, phenylindenyl, tolylindenyl, biphenylindenyl, naphthylindenyl, Tolylindenyl, benzylindenyl, dimethylindenyl, trimethylindenyl, tetramethylindenyl, diethylindenyl, triethylindenyl, tetraethylindenyl, dipropylindenyl, tripropylindenyl, tetrapropylindenyl, dibutylindenyl Nyl, tributylindenyl, tetrabutylindenyl, diphenylindenyl, methylphenylindenyl, methylnaphthylindenyl, methylanthrylindenyl, benzoindenyl, methylbenz Indenyl, dibenzo indenyl, and the like.
Of these, preferred are indenyl, methylindenyl, propylindenyl, tetramethylindenyl, tetraethylindenyl, tetrapropylindenyl, tetrabutylindenyl, phenylindenyl, naphthylindenyl, biphenylindenyl, and benzoindenyl. Nyl and dibenzoindenyl. Particularly preferred are indenyl, tetramethylindenyl, phenylindenyl, benzoindenyl and dibenzoindenyl.
M ¹ represents a transition metal of Group 4 of the periodic table.

In the transition metal compounds of the present invention (general formula ^{_{(2)), (C 5}} R 16 R 17 R 18 R 19 R 20), (C 5 R 21 R 22 R 23 R 24 R 25), and _(C 5 H ₂ R ²⁶ R ²⁷ R ²⁸ ) each represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ^{16 to} R ²⁸ are the same as those described above for the transition metal compound (general formula (1)). A structure similar to that of R ^{1 to} R ¹⁵ can be selected. However, at least one of R ^{16 to} R ²⁸ is a substituent other than a hydrogen atom. The M ² represents a periodic table group IV transition metals.
A preferred structure of the transition metal compound (general formula (2)) of the present invention is such that the substituents R ²⁶ , R ²⁷ and R ²⁸ of the substituted cyclopentadienyl group (C ₅ H ₂ R ²⁶ R ²⁷ R ²⁸ ) are 1 Is bonded to adjacent carbons at the 2-, 3- and 3-positions.

In the transition metal compounds of the present invention (general formula _{(3)), (C 5} H 2 R 29 R 30 R 31), (C 5 H 2 R 32 R 33 R 34), and _{(C 5} H ^{2 R 35 R 36} R ³⁷ ) represents a cyclopentadienyl group or a substituted cyclopentadienyl group, respectively, and R ^{29 to} R ³⁷ represent R ¹ shown in the description of the above-mentioned transition metal compound (general formula (1)). it can be selected the same structure as to R ^15. However, at least one of R ^{29 to} R ³⁷ is a substituent other than a hydrogen atom. M ³ represents a transition metal of Group 4 of the periodic table.
A preferred structure of the transition metal compound (general formula (3)) is a substituent R ²⁹ , R ³⁰ , R ^{31 of} each substituted cyclopentadienyl group, or R ³² , R ³³ , R ³⁴ , or R ³⁵ , R ³⁶ and R ³⁷ are bonded to adjacent carbons at the 1-, 2-, and 3-positions. Further preferred structures are the three substituted cyclopentadienyl ^{_{groups, (C 5 H 2 R 29}} R 30 R 31), (C 5 H 2 R 32 R 33 R 34), (C 5 H 2 R 35 R 36 R ³⁷ ) have the same structure.

In the transition metal compound (general formula (4)) of the present invention, (C ₅ H ₃ R ³⁸ R ³⁹ ), (C ₅ H ₃ R ⁴⁰ R ⁴¹ ), and (C ₅ H ₃ R ⁴² R ⁴³ ) are Each represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ represent a cyclopentadienyl group or a substituted cyclopentadienyl group, respectively. It represents an enyl group, and R ^{38 to} R ⁴³ can be selected from the same structures as R ^{1 to} R ¹⁵ described in the description of the transition metal compound (general formula (1)). However, at least one of R ^{38 to} R ⁴³ is a substituent other than a hydrogen atom. M ⁴ represents a transition metal of Group ⁴ of the periodic table.
Preferred structure of the transition metal compound (formula (4)), the three substituted cyclopentadienyl ^{_{groups, (C 5 H 3 R 38}} R 39), (C 5 H 3 R 40 R 41), and _{(C 5} H ₃ R ⁴² R ⁴³ ) have the same structure.

In the transition metal compound of the present invention (general formula (5)), (C ₉ R ⁴⁴ R ⁴⁵ R ⁴⁶ R ⁴⁷ R ⁴⁸ R ⁴⁹ R ⁵⁰ ), (C ₉ R ⁵¹ R ⁵² R ⁵³ R ⁵⁴ R ⁵⁵ R ⁵⁶ R) ⁵⁷ ) and (C ₉ R ⁵⁸ R ⁵⁹ R ⁶⁰ R ⁶¹ R ⁶² R ⁶³ R ⁶⁴ ) each represent an indenyl group or a substituted indenyl group, and R ^{44 to} R ⁶⁴ represent a hydrogen atom, a carbon atom having 1 to 30 carbon atoms. It is a hydrocarbon group or an organic silicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. A hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, which may be the same or different, but their carbon numbers are preferably 1 to 24. Preferably, it is particularly preferably 1 to 18. Examples of the hydrocarbon group of R ^{44 to} R ⁶⁴ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; Aryl groups such as dimethylphenyl, diethylphenyl, dipropylphenyl, dibutylphenyl, trimethylphenyl, triethylphenyl, tripropylphenyl, tributylphenyl, biphenyl, naphthyl, anthryl; trityl; And arylalkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylpropyl group, phenylbutyl group and neophyl group. These may have branches.
Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a vinyl group, an allyl group, and a phenyl group. Among these compounds, a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group are particularly preferred.
Examples of the organic silicon group having a hydrocarbon group having 1 to 30 carbon atoms represented by R ^{44 to} R ⁶⁴ as a substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. An alkylsilyl group having a substituent; an alkenylsilyl group having an alkenyl group such as a vinyl group or an allyl group as a substituent; a phenyl group, a dimethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a trimethylphenyl group; An arylsilyl group having an aryl group such as a triethylphenyl group, a tripropylphenyl group, a tributylphenyl group, a biphenyl group, a naphthyl group, an anthryl group as a substituent; a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylpropyl group; Ants such as phenylbutyl and neophyl An aryl alkyl silyl group having Ruarukiru group substituents. These may have branches.
Specific examples include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a trivinylsilyl group, a triallylsilyl group, and a triphenylsilyl group. Among these compounds, a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group are particularly preferred.
Further, among these ^R 44 ^{to R 50} or ^R 51 ^{to R 57,} or ^R 58 ^{to R 64} may be combined with each other to form a cyclic hydrocarbon group (including polycyclic structure).
Specific examples of the cyclic hydrocarbon group (including a polycyclic structure) formed by bonding to each other include benzoindenyl; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Alkenylbenzoindenyl having at least one alkyl group; alkenylbenzoindenyl having at least one alkenyl group such as vinyl group and allyl group; phenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl Arylbenzoindenyl having at least one aryl group such as a group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, styryl group, Benzhydryl group, phenylpropyl group, Arylalkyl benzoindenyl having at least one arylalkyl group such as enylbutyl group and neophyl group; dibenzoindenyl; alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group. Alkyldibenzoindenyl having one or more; alkenyldibenzoindenyl having one or more alkenyl groups such as vinyl group and allyl group; phenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, trimethylphenyl Dibenzoindenyl having at least one aryl group such as a group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, biphenyl group, naphthyl group, anthryl group; trityl group, phenethyl group, styryl group Benzhydryl group, phenylpropyl group, phenylbutyl group, etc. one or more having an arylalkyl dibenzo indenyl an arylalkyl group such as neophyl group. They may also have branches.
More specific examples include benzoindenyl, methylbenzoindenyl, dimethylbenzoindenyl, phenylbenzoindenyl, diphenylbenzoindenyl, dibenzoindenyl, methyldibenzoindenyl, dimethyldibenzoindenyl and the like.
Of these, benzoindenyl and dibenzoindenyl are preferred.
Incidentally, M ⁵ represents a periodic table group IV transition metals.

In the transition metal compound of the present invention (general formula (6)), (C ₉ H ₃ R ⁶⁵ R ⁶⁶ R ⁶⁷ R ⁶⁸ ), (C ₉ H ₃ R ⁶⁹ R ⁷⁰ R ⁷¹ R ⁷² ) and (C ₉ H ₃₎ R ⁷³ R ⁷⁴ R ⁷⁵ R ⁷⁶ ) represents an indenyl group or a substituted indenyl group, respectively, and R ^{65 to} R ⁷⁶ represent R ⁴⁴ to R ⁴⁴ described in the description of the aforementioned transition metal compound (general formula (5)). A structure similar to ⁶⁴ can be selected. M ⁴ represents a transition metal of Group ⁴ of the periodic table. Among them, R ^{65 to} R ⁶⁸ , R ^{69 to} R ⁷² , and R ^{73 to} R ⁷⁶ are bonded to the 4-, 5-, 6-, and 7-positions (6-membered ring portions) of the respective indenyl groups. May be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure).
Preferred structures of the transition metal compound (general formula (6)) include three substituted indenyl groups (C ₉ H ₃ R ⁶⁵ R ⁶⁶ R ⁶⁷ R ⁶⁸ ), (C ₉ H ₃ R ⁶⁹ R ⁷⁰ R ⁷¹ R ⁷² ) and (C ₉ H ₃ R ⁷³ R ⁷⁴ R ⁷⁵ R ⁷⁶ ) have the same structure.

  Specific examples of the transition metal of Group 4 of the periodic table of the transition metal compound of the present invention include Ti, Zr, and Hf. Among these, Ti and Zr are preferred, and Zr is particularly preferred.

Specific examples of the transition metal compound of the present invention are shown below, but it should not be construed that the invention is limited thereto.
Cp ₂ (MeCp) ZrH, Cp ₂ (EtCp) ZrH, Cp ₂ (PrCp) ZrH, Cp ₂ (BuCp) ZrH, Cp ₂ (PhCp) ZrH, Cp ₂ (Me ₂ Cp) ZrH, Cp ₂ (MeEtCp) ZrH, Cp ₂ (MePrCp) ZrH, Cp ₂ (MeBuCp) ZrH, Cp ₂ (MePhCp) ZrH, Cp ₂ (Et ₂ Cp) ZrH, Cp ₂ (Me ₃ SiCp) ZrH, Cp ₂ (Et ₃ SiCp) ZrH, Cp ₂ (Ph ₃ SiCp) ZrH, Cp ₂ ((Me ₃ Si) ₂ Cp) ZrH, Cp ₂ (Me ₃ Cp) ZrH, Cp ₂ (Et ₃ Cp) ZrH, Cp ₂ (Pr ₃ Cp) ZrH, Cp ₂ (Bu ₃ Cp) ZrH, Cp ₂ (Me ₄ Cp) ZrH, Cp ₂ (Et ₄ Cp) ZrH, Cp ₂ (Pr ₄ Cp) ZrH, Cp ₂ (Bu ₄ Cp) ZrH, Cp ₂ (Me ₅ Cp) ZrH, (MeCp) ₂ (Cp) ZrH, (MeCp) ₂ (EtCp) ZrH, (MeCp) ₂ (PrCp) ZrH, (MeCp) ₂ (BuCp) ZrH, (MeCp) ₂ (PhCp) ZrH, (MeCp) ₂ (Me ₂ Cp) ZrH, (MeCp) ₂ (MeEtCp) ZrH, (MeCp) ₂ (MePrCp) ZrH, (MeCp) ₂ (MeBuCp) ZrH, (MeCp) ₂ (MePhCp) ZrH, (MeCp) ₂ (Et ₂ Cp) ZrH, (MeCp) ₂ (Me ₃ (SiCp) ZrH, (MeCp) ₂ (Et ₃ (SiCp) ZrH, (MeCp) ₂ (Ph ₃ (SiCp) ZrH, (MeCp) ₂ ((Me ₃ Si) ₂ Cp) ZrH, (MeCp) ₂ (Me ₃ Cp) ZrH, (MeCp) ₂ (Et ₃ Cp) ZrH, (MeCp) ₂ (Pr ₃ Cp) ZrH, (MeCp) ₂ (Bu ₃ Cp) ZrH, (MeCp) ₂ (Me ₄ Cp) ZrH, (MeCp) ₂ (Et ₄ Cp) ZrH, (MeCp) ₂ (Pr ₄ Cp) ZrH, (MeCp) ₂ (Bu ₄ Cp) ZrH, (MeCp) ₂ (Me ₅ Cp) ZrH, (BuCp) ₂ (Cp) ZrH, (BuCp) ₂ (MeCp) ZrH, (BuCp) ₂ (EtCp) ZrH, (BuCp) ₂ (PrCp) ZrH, (BuCp) ₂ (PhCp) ZrH, (BuCp) ₂ (Me ₂ Cp) ZrH, (BuCp) ₂ (MeEtCp) ZrH, (BuCp) ₂ (MePrCp) ZrH, (BuCp) ₂ (MeBuCp) ZrH, (BuCp) ₂ (MePhCp) ZrH, (BuCp) ₂ (Et ₂ Cp) ZrH, (BuCp) ₂ (Me ₃ (SiCp) ZrH, (BuCp) ₂ (Et ₃ (SiCp) ZrH, (BuCp) ₂ (Ph ₃ (SiCp) ZrH, (BuCp) ₂ ((Me ₃ Si) ₂ Cp) ZrH, (BuCp) ₂ (Me ₃ Cp) ZrH, (BuCp) ₂ (Et ₃ Cp) ZrH, (BuCp) ₂ (Pr ₃ Cp) ZrH, (BuCp) ₂ (Bu ₃ Cp) ZrH, (BuCp) ₂ (Me ₄ Cp) ZrH, (BuCp) ₂ (Et ₄ Cp) ZrH, (BuCp) ₂ (Pr ₄ Cp) ZrH, (BuCp) ₂ (Bu ₄ Cp) ZrH, (BuCp) ₂ (Me ₅ Cp) ZrH, (Me ₃ SiCp) ₂ (Cp) ZrH, (Me ₃ SiCp) ₂ (MeCp) ZrH, (Me ₃ SiCp) ₂ (EtCp) ZrH, (Me ₃ SiCp) ₂ (PrCp) ZrH, (Me ₃ SiCp) ₂ (BuCp) ZrH, (Me ₃ SiCp) ₂ (PhCp) ZrH, (Me ₃ SiCp) ₂ (Me ₂ Cp) ZrH, (Me ₃ SiCp) ₂ (MeEtCp) ZrH, (Me ₃ SiCp) ₂ (MePrCp) ZrH, (Me ₃ SiCp) ₂ (MeBuCp) ZrH, (Me ₃ SiCp) ₂ (MePhCp) ZrH, (Me ₃ SiCp) ₂ (Et ₂ Cp) ZrH, (Me ₃ SiCp) ₂ (Et ₃ (SiCp) ZrH, (Me ₃ SiCp) ₂ (Ph ₃ (SiCp) ZrH, (Me ₃ SiCp) ₂ ((Me ₃ Si) ₂ Cp) ZrH, (Me ₃ SiCp) ₂ (Me ₃ Cp) ZrH, (Me ₃ SiCp) ₂ (Et ₃ Cp) ZrH, (Me ₃ SiCp) ₂ (Pr ₃ Cp) ZrH, (Me ₃ SiCp) ₂ (Bu ₃ Cp) ZrH, (Me ₃ SiCp) ₂ (Me ₄ Cp) ZrH, (Me ₃ SiCp) ₂ (Et ₄ Cp) ZrH, (Me ₃ SiCp) ₂ (Pr ₄ Cp) ZrH, (Me ₃ SiCp) ₂ (Bu ₄ Cp) ZrH, (Me ₃ SiCp) ₂ (Me ₅ Cp) ZrH, (Me ₂ Cp) ₂ (Cp) ZrH, (Me ₂ Cp) ₂ (MeCp) ZrH, (Me ₂ Cp) ₂ (EtCp) ZrH, (Me ₂ Cp) ₂ (PrCp) ZrH, (Me ₂ Cp) ₂ (BuCp) ZrH, (Me ₂ Cp) ₂ (PhCp) ZrH, (Me ₂ Cp) ₂ (MeEtCp) ZrH, (Me ₂ Cp) ₂ (MePrCp) ZrH, (Me ₂ Cp) ₂ (MeBuCp) ZrH, (Me ₂ Cp) ₂ (MePhCp) ZrH, (Me ₂ Cp) ₂ (Et ₂ Cp) ZrH, (Me ₂ Cp) ₂ (Et ₃ (SiCp) ZrH, (Me ₂ Cp) ₂ (Ph ₃ (SiCp) ZrH, (Me ₂ Cp) ₂ ((Me ₃ Si) ₂ Cp) ZrH, (Me ₂ Cp) ₂ (Me ₃ Cp) ZrH, (Me ₂ Cp) ₂ (Et ₃ Cp) ZrH, (Me ₂ Cp) ₂ (Pr ₃ Cp) ZrH, (Me ₂ Cp) ₂ (Bu ₃ Cp) ZrH, (Me ₂ Cp) ₂ (Me ₄ Cp) ZrH, (Me ₂ Cp) ₂ (Et ₄ Cp) ZrH, (Me ₂ Cp) ₂ (Pr ₄ Cp) ZrH, (Me ₂ Cp) ₂ (Bu ₄ Cp) ZrH, (Me ₂ Cp) ₂ (Me ₅ Cp) ZrH, (Me ₃ Cp) ₂ (Cp) ZrH, (Me ₃ Cp) ₂ (MeCp) ZrH, (Me ₃ Cp) ₂ (EtCp) ZrH, (Me ₃ Cp) ₂ (PrCp) ZrH, (Me ₃ Cp) ₂ (BuCp) ZrH, (Me ₃ Cp) ₂ (PhCp) ZrH, (Me ₃ Cp) ₂ (Me ₂ Cp) ZrH, (Me ₃ Cp) ₂ (MeEtCp) ZrH, (Me ₃ Cp) ₂ (MePrCp) ZrH, (Me ₃ Cp) ₂ (MeBuCp) ZrH, (Me ₃ Cp) ₂ (MePhCp) ZrH, (Me ₃ Cp) ₂ (Et ₂ Cp) ZrH, (Me ₃ Cp) ₂ (Et ₃ (SiCp) ZrH, (Me ₃ Cp) ₂ (Ph ₃ (SiCp) ZrH, (Me ₃ Cp) ₂ ((Me ₃ Si) ₂ Cp) ZrH, (Me ₃ Cp) ₂ (Et ₃ Cp) ZrH, (Me ₃ Cp) ₂ (Pr ₃ Cp) ZrH, (Me ₃ Cp) ₂ (Bu ₃ Cp) ZrH, (Me ₃ Cp) ₂ (Me ₄ Cp) ZrH, (Me ₃ Cp) ₂ (Et ₄ Cp) ZrH, (Me ₃ Cp) ₂ (Pr ₄ Cp) ZrH, (Me ₃ Cp) ₂ (Bu ₄ Cp) ZrH, (Me ₃ Cp) ₂ (Me ₅ Cp) ZrH, (MeCp) ₃ ZrH, (EtCp) ₃ ZrH, (PrCp) ₃ ZrH, (BuCp) ₃ ZrH, (PhCp) ₃ ZrH, (Me ₃ SiCp) ₃ ZrH, (Et ₃ SiCp) ₃ ZrH, (Ph ₃ SiCp) ₃ ZrH, (Me ₂ Cp) ₃ ZrH, (Et ₂ Cp) ₃ ZrH, (Pr ₂ Cp) ₃ ZrH, (Bu ₂ Cp) ₃ ZrH, (Me ₃ Cp) ₃ ZrH, (Et ₃ Cp) ₃ ZrH, (Pr ₃ Cp) ₃ ZrH, (Bu ₃ Cp) ₃ ZrH, (Me ₄ Cp) ₃ ZrH, (Et ₄ Cp) ₃ ZrH, (Pr ₄ Cp) ₃ ZrH, (Bu ₄ Cp) ₃ ZrH, (Me ₅ Cp) ₃ ZrH, (Et ₅ Cp) ₃ ZrH, (Pr ₅ Cp) ₃ ZrH, (Bu ₅ Cp) ₃ ZrH, Ind ₂ (Cp) ZrH, Ind ₂ (MeCp) ZrH, Ind ₂ (EtCp) ZrH, Ind ₂ (PrCp) ZrH, Ind ₂ (BuCp) ZrH, Ind ₂ (PhCp) ZrH, Ind ₂ (Me ₂ Cp) ZrH, Ind ₂ (MeEtCp) ZrH, Ind ₂ (MePrCp) ZrH, Ind ₂ (MeBuCp) ZrH, Ind ₂ (MePhCp) ZrH, Ind ₂ (Et ₂ Cp) ZrH, Ind ₂ (Me ₃ SiCp) ZrH, Ind ₂ (Et ₃ SiCp) ZrH,
Ind ₂ (Ph ₃ SiCp) ZrH, Ind ₂ ((Me ₃ Si) ₂ Cp) ZrH, Ind ₂ (Me ₃ Cp) ZrH, Ind ₂ (Et ₃ Cp) ZrH, Ind ₂ (Pr ₃ Cp) ZrH, Ind ₂ (Bu ₃ Cp) ZrH, Ind ₂ (Me ₄ Cp) ZrH, Ind ₂ (Et ₄ Cp) ZrH, Ind ₂ (Pr ₄ Cp) ZrH, Ind ₂ (Bu ₄ Cp) ZrH, Ind ₂ (Me ₅ (Cp) ZrH, (Cp) (Ind) (MeCp) ZrH, (Cp) (Ind) (EtCp) ZrH, (Cp) (Ind) (PrCp) ZrH, (Cp) (Ind) (BuCp) ZrH, (Cp) ) (Ind) (PhCp) ZrH, (Cp) (Ind) (Me ₂ (Cp) ZrH, (Cp) (Ind) (MeEtCp) ZrH, (Cp) (Ind) (MePrCp) ZrH, (Cp) (Ind) (MeBuCp) ZrH, (Cp) (Ind) (MePhCp) ZrH, (Cp) ) (Ind) (Et ₂ Cp) ZrH, (Cp) (Ind) (Me ₃ (SiCp) ZrH, (Cp) (Ind) (Et ₃ (SiCp) ZrH, (Cp) (Ind) (Ph ₃ (SiCp) ZrH, (Cp) (Ind) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (Ind) (Me ₃ Cp) ZrH, (Cp) (Ind) (Et ₃ Cp) ZrH, (Cp) (Ind) (Pr ₃ Cp) ZrH, (Cp) (Ind) (Bu ₃ Cp) ZrH, (Cp) (Ind) (Me ₄ Cp) ZrH, (Cp) (Ind) (Et ₄ Cp) ZrH, (Cp) (Ind) (Pr ₄ Cp) ZrH, (Cp) (Ind) (Bu ₄ Cp) ZrH, (Cp) (Ind) (Me ₅ Cp) ZrH, MeInd ₂ (Cp) ZrH, MeInd ₂ (MeCp) ZrH, MeInd ₂ (EtCp) ZrH, MeInd ₂ (PrCp) ZrH, MeInd ₂ (BuCp) ZrH, MeInd ₂ (PhCp) ZrH, MeInd ₂ (Me ₂ Cp) ZrH, MeInd ₂ (MeEtCp) ZrH, MeInd ₂ (MePrCp) ZrH, MeInd ₂ (MeBuCp) ZrH, MeInd ₂ (MePhCp) ZrH, MeInd ₂ (Et ₂ Cp) ZrH, MeInd ₂ (Me ₃ SiCp) ZrH, MeInd ₂ (Et ₃ SiCp) ZrH, MeInd ₂ (Ph ₃ SiCp) ZrH, MeInd ₂ ((Me ₃ Si) ₂ Cp) ZrH, MeInd ₂ (Me ₃ Cp) ZrH, MeInd ₂ (Et ₃ Cp) ZrH, MeInd ₂ (Pr ₃ Cp) ZrH, MeInd ₂ (Bu ₃ Cp) ZrH, MeInd ₂ (Me ₄ Cp) ZrH, MeInd ₂ (Et ₄ Cp) ZrH, MeInd ₂ (Pr ₄ Cp) ZrH, MeInd ₂ (Bu ₄ Cp) ZrH, MeInd ₂ (Me ₅ (Cp) ZrH, (Cp) (MeInd) (MeCp) ZrH, (Cp) (MeInd) (EtCp) ZrH, (Cp) (MeInd) (PrCp) ZrH, (Cp) (MeInd) (BuCp) ZrH, (Cp) ) (MeInd) (PhCp) ZrH, (Cp) (MeInd) (Me ₂ (Cp) ZrH, (Cp) (MeInd) (MeEtCp) ZrH, (Cp) (MeInd) (MePrCp) ZrH, (Cp) (MeInd) (MeBuCp) ZrH, (Cp) (MeInd) (MePhCp) ZrH, ) (MeInd) (Et ₂ Cp) ZrH, (Cp) (MeInd) (Me ₃ (SiCp) ZrH, (Cp) (MeInd) (Et ₃ (SiCp) ZrH, (Cp) (MeInd) (Ph ₃ (SiCp) ZrH, (Cp) (MeInd) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (MeInd) (Me ₃ Cp) ZrH, (Cp) (MeInd) (Et ₃ Cp) ZrH, (Cp) (MeInd) (Pr ₃ Cp) ZrH, (Cp) (MeInd) (Bu ₃ Cp) ZrH, (Cp) (MeInd) (Me ₄ Cp) ZrH, (Cp) (MeInd) (Et ₄ Cp) ZrH, (Cp) (MeInd) (Pr ₄ Cp) ZrH, (Cp) (MeInd) (Bu ₄ Cp) ZrH, (Cp) (MeInd) (Me ₅ Cp) ZrH, PhInd ₂ (Cp) ZrH, PhInd ₂ (MeCp) ZrH, PhInd ₂ (EtCp) ZrH, PhInd ₂ (PrCp) ZrH, PhInd ₂ (BuCp) ZrH, PhInd ₂ (PhCp) ZrH, PhInd ₂ (Me ₂ Cp) ZrH, PhInd ₂ (MeEtCp) ZrH, PhInd ₂ (MePrCp) ZrH, PhInd ₂ (MeBuCp) ZrH, PhInd ₂ (MePhCp) ZrH, PhInd ₂ (Et ₂ Cp) ZrH, PhInd ₂ (Me ₃ SiCp) ZrH, PhInd ₂ (Et ₃ SiCp) ZrH, PhInd ₂ (Ph ₃ SiCp) ZrH, PhInd ₂ ((Me ₃ Si) ₂ Cp) ZrH, PhInd ₂ (Me ₃ Cp) ZrH, PhInd ₂ (Et ₃ Cp) ZrH, PhInd ₂ (Pr ₃ Cp) ZrH, PhInd ₂ (Bu ₃ Cp) ZrH, PhInd ₂ (Me ₄ Cp) ZrH, PhInd ₂ (Et ₄ Cp) ZrH, PhInd ₂ (Pr ₄ Cp) ZrH, PhInd ₂ (Bu ₄ Cp) ZrH, PhInd ₂ (Me ₅ (Cp) ZrH, (Cp) (PhInd) (MeCp) ZrH, (Cp) (PhInd) (EtCp) ZrH, (Cp) (PhInd) (PrCp) ZrH, (Cp) (PhInd) (BuCp) ZrH, (Cp) ) (PhInd) (PhCp) ZrH, (Cp) (PhInd) (Me ₂ (Cp) ZrH, (Cp) (PhInd) (MeEtCp) ZrH, (Cp) (PhInd) (MePrCp) ZrH, (Cp) (PhInd) (MeBuCp) ZrH, (Cp) (PhInd) (MePhCp) ZrH, (Cr) ) (PhInd) (Et ₂ Cp) ZrH, (Cp) (PhInd) (Me ₃ (SiCp) ZrH, (Cp) (PhInd) (Et ₃ (SiCp) ZrH, (Cp) (PhInd) (Ph ₃ (SiCp) ZrH, (Cp) (PhInd) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (PhInd) (Me ₃ Cp) ZrH, (Cp) (PhInd) (Et ₃ Cp) ZrH, (Cp) (PhInd) (Pr ₃ Cp) ZrH, (Cp) (PhInd) (Bu ₃ Cp) ZrH, (Cp) (PhInd) (Me ₄ Cp) ZrH, (Cp) (PhInd) (Et ₄ Cp) ZrH, (Cp) (PhInd) (Pr ₄ Cp) ZrH, (Cp) (PhInd) (Bu ₄ Cp) ZrH, (Cp) (PhInd) (Me ₅ Cp) ZrH, Me ₄ Ind ₂ (Cp) ZrH, Me ₄ Ind ₂ (MeCp) ZrH, Me ₄ Ind ₂ (EtCp) ZrH, Me ₄ Ind ₂ (PrCp) ZrH, Me ₄ Ind ₂ (BuCp) ZrH, Me ₄ Ind ₂ (PhCp) ZrH, Me ₄ Ind ₂ (Me ₂ Cp) ZrH, Me ₄ Ind ₂ (MeEtCp) ZrH, Me ₄ Ind ₂ (MePrCp) ZrH, Me ₄ Ind ₂ (MeBuCp) ZrH, Me ₄ Ind ₂ (MePhCp) ZrH, Me ₄ Ind ₂ (Et ₂ Cp) ZrH, Me ₄ Ind ₂ (Me ₃ SiCp) ZrH, Me ₄ Ind ₂ (Et ₃ SiCp) ZrH, Me ₄ Ind ₂ (Ph ₃ SiCp) ZrH, Me ₄ Ind ₂ ((Me ₃ Si) ₂ Cp) ZrH, Me ₄ Ind ₂ (Me ₃ Cp) ZrH, Me ₄ Ind ₂ (Et ₃ Cp) ZrH, Me ₄ Ind ₂ (Pr ₃ Cp) ZrH, Me ₄ Ind ₂ (Bu ₃ Cp) ZrH, Me ₄ Ind ₂ (Me ₄ Cp) ZrH, Me ₄ Ind ₂ (Et ₄ Cp) ZrH, Me4Ind ₂ (Pr ₄ Cp) ZrH, Me4Ind ₂ (Bu ₄ Cp) ZrH, Me4Ind ₂ (Me ₅ Cp) ZrH, (Cp) (Me ₄ Ind) (MeCp) ZrH, (Cp) (Me ₄ Ind) (EtCp) ZrH, (Cp) (Me ₄ Ind) (PrCp) ZrH, (Cp) (Me ₄ Ind) (BuCp) ZrH, (Cp) (Me ₄ Ind) (PhCp) ZrH, (Cp) (Me ₄ Ind) (Me ₂ Cp) ZrH, (Cp) (Me ₄ Ind) (MeEtCp) ZrH, (Cp) (Me ₄ Ind) (MePrCp) ZrH, (Cp) (Me ₄ Ind) (MeBuCp) ZrH, (Cp) (Me ₄ Ind) (MePhCp) ZrH, (Cp) (Me ₄ Ind) (Et ₂ Cp) ZrH, (Cp) (Me ₄ Ind) (Me ₃ (SiCp) ZrH, (Cp) (Me ₄ Ind) (Et ₃ (SiCp) ZrH, (Cp) (Me ₄ Ind) (Ph ₃ (SiCp) ZrH, (Cp) (Me ₄ Ind) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (Me ₄ Ind) (Me ₃ Cp) ZrH, (Cp) (Me ₄ Ind) (Et ₃ Cp) ZrH, (Cp) (Me ₄ Ind) (Pr ₃ Cp) ZrH, (Cp) (Me ₄ Ind) (Bu ₃ Cp) ZrH, (Cp) (Me ₄ Ind) (Me ₄ Cp) ZrH, (Cp) (Me ₄ Ind) (Et ₄ Cp) ZrH, (Cp) (Me ₄ Ind) (Pr ₄ Cp) ZrH, (Cp) (Me ₄ Ind) (Bu ₄ Cp) ZrH, (Cp) (Me ₄ Ind) (Me ₅ Cp) ZrH, BenzInd ₂ (Cp) ZrH, BenzInd ₂ (MeCp) ZrH, BenzInd ₂ (EtCp) ZrH, BenzInd ₂ (PrCp) ZrH,
BenzInd ₂ (BuCp) ZrH, BenzInd ₂ (PhCp) ZrH, BenzInd ₂ (Me ₂ Cp) ZrH, BenzInd ₂ (MeEtCp) ZrH, BenzInd ₂ (MePrCp) ZrH, BenzInd ₂ (MeBuCp) ZrH, BenzInd ₂ (MePhCp) ZrH, BenzInd ₂ (Et ₂ Cp) ZrH, BenzInd ₂ (Me ₃ SiCp) ZrH, BenzInd ₂ (Et ₃ SiCp) ZrH, BenzInd ₂ (Ph ₃ SiCp) ZrH, BenzInd ₂ ((Me ₃ Si) ₂ Cp) ZrH, BenzInd ₂ (Me ₃ Cp) ZrH, BenzInd ₂ (Et ₃ Cp) ZrH, BenzInd ₂ (Pr ₃ Cp) ZrH, BenzInd ₂ (Bu ₃ Cp) ZrH, BenzInd ₂ (Me ₄ Cp) ZrH, BenzInd ₂ (Et ₄ Cp) ZrH, BenzInd ₂ (Pr ₄ Cp) ZrH, BenzInd ₂ (Bu ₄ Cp) ZrH, BenzInd ₂ (Me ₅ (Cp) ZrH, (Cp) (BenzInd) (MeCp) ZrH, (Cp) (BenzInd) (EtCp) ZrH, (Cp) (BenzInd) (PrCp) ZrH, (Cp) (BenzInd) (BuCp) ZrH, (Cp) ) (BenzInd) (PhCp) ZrH, (Cp) (BenzInd) (Me ₂ (Cp) ZrH, (Cp) (BenzInd) (MeEtCp) ZrH, (Cp) (BenzInd) (MePrCp) ZrH, (Cp) (BenzInd) (MeBuCp) ZrH, (Cp) (BenzInd) (MePhCpHr) ) (BenzInd) (Et ₂ Cp) ZrH, (Cp) (BenzInd) (Me ₃ (SiCp) ZrH, (Cp) (BenzInd) (Et ₃ (SiCp) ZrH, (Cp) (BenzInd) (Ph ₃ (SiCp) ZrH, (Cp) (BenzInd) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (BenzInd) (Me ₃ Cp) ZrH, (Cp) (BenzInd) (Et ₃ Cp) ZrH, (Cp) (BenzInd) (Pr ₃ Cp) ZrH, (Cp) (BenzInd) (Bu ₃ Cp) ZrH, (Cp) (BenzInd) (Me ₄ Cp) ZrH, (Cp) (BenzInd) (Et ₄ Cp) ZrH, (Cp) (BenzInd) (Pr ₄ Cp) ZrH, (Cp) (BenzInd) (Bu ₄ Cp) ZrH, (Cp) (BenzInd) (Me ₅ Cp) ZrH, DibenzoInd ₂ (Cp) ZrH, DibenzoInd ₂ (MeCp) ZrH, DibenzoInd ₂ (EtCp) ZrH, DibenzoInd ₂ (PrCp) ZrH, DibenzoInd ₂ (BuCp) ZrH, DibenzoInd ₂ (PhCp) ZrH, DibenzoInd ₂ (Me ₂ Cp) ZrH, DibenzoInd ₂ (MeEtCp) ZrH, DibenzoInd ₂ (MePrCp) ZrH, DibenzoInd ₂ (MeBuCp) ZrH, DibenzoInd ₂ (MePhCp) ZrH, DibenzoInd ₂ (Et ₂ Cp) ZrH, DibenzoInd ₂ (Me ₃ SiCp) ZrH, DibenzoInd ₂ (Et ₃ SiCp) ZrH, DibenzoInd ₂ (Ph ₃ SiCp) ZrH, DibenzoInd ₂ ((Me ₃ Si) ₂ Cp) ZrH, DibenzoInd ₂ (Me ₃ Cp) ZrH, DibenzoInd ₂ (Et ₃ Cp) ZrH, DibenzoInd ₂ (Pr ₃ Cp) ZrH, DibenzoInd ₂ (Bu ₃ Cp) ZrH, DibenzoInd ₂ (Me ₄ Cp) ZrH, DibenzoInd ₂ (Et ₄ Cp) ZrH, DibenzoInd ₂ (Pr ₄ Cp) ZrH, DibenzoInd ₂ (Bu ₄ Cp) ZrH, DibenzoInd ₂ (Me ₅ (Cp) ZrH, (Cp) (DibenzoInd) (MeCp) ZrH, (Cp) (DibenzoInd) (EtCp) ZrH, (Cp) (DibenzoInd) (PrCp) ZrH, (Cp) (DibenzoInd) (HuCp) ) (DibenzoInd) (PhCp) ZrH, (Cp) (DibenzoInd) (Me ₂ (Cp) ZrH, (Cp) (DibenzoInd) (MeEtCp) ZrH, (Cp) (DibenzoInd) (MePrCp) ZrH, (Cp) (DibenzoInd) (MeBuCp) ZrH, (Cp) (CbenZPhd) ) (DibenzoInd) (Et ₂ Cp) ZrH, (Cp) (DibenzoInd) (Me ₃ (SiCp) ZrH, (Cp) (DibenzoInd) (Et ₃ (SiCp) ZrH, (Cp) (DibenzoInd) (Ph ₃ (SiCp) ZrH, (Cp) (DibenzoInd) ((Me ₃ Si) ₂ Cp) ZrH, (Cp) (DibenzoInd) (Me ₃ Cp) ZrH, (Cp) (DibenzoInd) (Et ₃ Cp) ZrH, (Cp) (DibenzoInd) (Pr ₃ Cp) ZrH, (Cp) (DibenzoInd) (Bu ₃ Cp) ZrH, (Cp) (DibenzoInd) (Me ₄ Cp) ZrH, (Cp) (DibenzoInd) (Et ₄ Cp) ZrH, (Cp) (DibenzoInd) (Pr ₄ Cp) ZrH, (Cp) (DibenzoInd) (Bu ₄ Cp) ZrH, (Cp) (BenzInd) (Me ₅ Cp) ZrH, Ind ₃ ZrH, Ind ₂ (MeInd) ZrH, Ind ₂ (EtInd) ZrH, Ind ₂ (PrInd) ZrH, Ind ₂ (BuInd) ZrH, Ind ₂ (Me ₃ SiInd) ZrH, Ind ₂ (Me ₂ Ind) ZrH, Ind ₂ (Et ₂ Ind) ZrH, Ind ₂ (Pr ₂ Ind) ZrH, Ind ₂ (Bu ₂ Ind) ZrH, Ind ₂ (Me ₄ Ind) ZrH, Ind ₂ (Et ₄ Ind) ZrH, Ind ₂ (Pr ₄ Ind) ZrH, Ind ₂ (Bu ₄ Ind) ZrH, Ind ₂ (NaphInd) ZrH, Ind ₂ (BiPhInd) ZrH, (MeInd) ₃ ZrH, (EtInd) ₃ ZrH, (PrInd) ₃ ZrH, (BuInd) ₃ ZrH, (Me ₃ SiInd) ₃ ZrH, (PhInd) ₃ ZrH, (NaphInd) ₃ ZrH, (BiPhInd) ₃ ZrH, (Me ₂ Ind) ₃ ZrH, (Et ₂ Ind) ₃ ZrH, (Pr ₂ Ind) ₃ ZrH, (Bu ₂ Ind) ₃ ZrH, (Me ₂ Ind) ₂ (Ind) ZrH, (Et ₂ Ind) ₂ (Ind) ZrH, (Pr ₂ Ind) ₂ (Ind) ZrH, (Bu ₂ Ind) ₂ (Ind) ZrH, (Ph ₂ Ind) ₂ (Ind) ZrH, (Me ₃ Ind) ₃ ZrH, (Et ₃ Ind) ₃ ZrH, (Pr ₃ Ind) ₃ ZrH, (Bu ₃ Ind) ₃ ZrH, (Me ₄ Ind) ₃ ZrH, (Et ₄ Ind) ₃ ZrH, (Pr ₄ Ind) ₃ ZrH, (Bu ₄ Ind) ₃ ZrH, (BenzInd) ₃ ZrH, (BenzInd) ₂ (Ind) ZrH, (BenzInd) (Ind) ₂ ZrH, (DibenzoInd) ₂ (Ind) ZrH, (DibenzoInd) (Ind) ₂ ZrH, (DibenzoInd) ₃ ZrH, (BenzInd) ₂ (DibenzoInd) ZrH, (BenzInd) (DibenzoInd) ₂ ZrH, (DibenzoInd) (BenzInd) (Ind) ZrH.
Here, the following abbreviations were used in the above structural formulas (the same applies hereinafter). Cp = cyclopentadienyl, MeCp = methylcyclopentadienyl, EtCp = ethylcyclopentadienyl, PrCp = propylcyclopentadienyl, BuCp = butylcyclopentadienyl, PhCp = phenylcyclopentadienyl, Me ₂ Cp = dimethylcyclopentadienyl, MeEtCp = methylethylcyclopentadienyl, MePrCp = methylpropylcyclopentadienyl, MeBuCp = methylbutylcyclopentadienyl, MePhCp = methylphenylcyclopentadienyl, Et ₂ Cp = diethylcyclopentadienyl, Me ₃ SiCp = trimethylsilylcyclopentadienyl, Et ₃ SiCp = triethylsilylcyclopentadienyl, Ph ₃ SiCp = triphenylsilylcyclopentadienyl, (Me ₃ Si) ₂ Cp = bistrimethylsilylcyclopentadienyl, Me ₃ Cp = trimethylcyclopentadienyl, Et ₃ Cp = triethylcyclopentadienyl, Pr ₃ Cp = tripropylcyclopentadienyl, Bu ₃ Cp = tributylcyclopentadienyl, Me ₄ Cp = tetramethylcyclopentadienyl, Et ₄ Cp = tetraethylcyclopentadienyl, Pr ₄ Cp = tetrapropylcyclopentadienyl, Bu ₄ Cp = tetrabutylcyclopentadienyl, Me ₅ Cp = pentamethylcyclopentadienyl, Ind = indenyl, MeInd = methylindenyl, EtInd = ethylindenyl, PrInd = propylindenyl, BuInd = butylindenyl, Me ₃ SiInd = trimethylsilylindenyl, PhInd = phenylindenyl, NaphInd = naphthylindene, BiPhInd = biphenylindene, Me ₂ Ind = dimethylindenyl, Et ₂ Ind = diethylindenyl, Pr ₂ Ind = dipropylindenyl, Bu ₂ Ind = dibutylindenyl, Me ₃ Ind = trimethylindenyl, Et ₃ Ind = triethylindenyl, Pr ₃ Ind = tripropylindenyl, Bu ₃ Ind = tributylindenyl, Me ₄ Ind = tetramethylindenyl, Et ₄ Ind = tetraethylindenyl, Pr ₄ Ind = tetrapropylindenyl, Bu ₄ Ind = tetrabutylindenyl, BenzInd = benzoindenyl, and DibenzoInd = dibenzoindenyl, respectively.
When these compounds are used as catalyst components for olefin polymerization, two or more of these compounds can be used.

Among the specific compounds exemplified above, preferable ones as catalyst components for olefin polymerization are shown below.
_{That, Cp 2 (MeCp) ZrH,} Cp 2 (PrCp) ZrH, Cp 2 (BuCp) ZrH, Cp 2 (Me 2 Cp) ZrH, Cp 2 (MePrCp) ZrH, Cp 2 (MeBuCp) ZrH, Cp 2 (Me _{3 SiCp) ZrH, Cp 2 (} Me 3 Cp) ZrH, (MeCp) 2 (Cp) ZrH, (MeCp) 2 (PrCp) ZrH, (MeCp) 2 (BuCp) ZrH, (MeCp) 2 (Me 2 Cp) _{ZrH, (MeCp) 2 (MePrCp} ) ZrH, (MeCp) 2 (MeBuCp) ZrH, (MeCp) 2 (Me 3 SiCp) ZrH, (MeCp) 2 (Me 3 Cp) ZrH, (BuCp) 2 (Cp) ZrH _{, (BuCp) 2 (MeCp)} ZrH, (BuCp) 2 (PrCp) ZrH, (BuCp) _{(Me 2 Cp) ZrH, (} BuCp) 2 (MePrCp) ZrH, (BuCp) 2 (MeBuCp) ZrH, (BuCp) 2 (Me 3 SiCp) ZrH, (Me 3 SiCp) 2 (Cp) ZrH, (Me 3 (SiCp) ₂ (MeCp) ZrH, (Me ₃ SiCp) ₂ (PrCp) ZrH, (Me ₃ SiCp) ₂ (BuCp) ZrH, (Me ₃ SiCp) ₂ (Me ₂ Cp) ZrH, (Me ₃ SiCp) _{2 MePrCp) ZrH, (Me 3 SiCp} ) 2 (MeBuCp) ZrH, (Me 3 SiCp) 2 (Me 3 Cp) ZrH, (Me 2 Cp) 2 (Cp) ZrH, (Me 2 Cp) 2 (MeCp) ZrH, _{(Me 2 Cp) 2 (PrCp} ) ZrH, (Me 2 Cp) 2 (BuCp) ZrH, (Me 2 Cp) _{(MePrCp) ZrH, (Me 2} Cp) 2 (MeBuCp) ZrH, (Me 2 Cp) 2 (Me 3 Cp) ZrH, (Me 3 Cp) 2 (Cp) ZrH, (MeCp) 3 ZrH, (EtCp) 3 _{ZrH, (PrCp) 3 ZrH,} (BuCp) 3 ZrH, (PhCp) 3 ZrH, (Me 3 SiCp) 3 ZrH, (Et 3 SiCp) 3 ZrH, (Me 2 Cp) 3 ZrH, (Me 3 Cp) 3 _{ZrH, (Me 4 Cp) 3} ZrH, (Me 5 Cp) 3 ZrH, Ind 2 (Cp) ZrH, Ind 2 (MeCp) ZrH, Ind 2 (PrCp) ZrH, Ind 2 (BuCp) ZrH, Ind 2 (Me ₂ Cp) ZrH, Ind ₂ (MePrCp) ZrH, Ind ₂ (MeBuCp) ZrH, Ind ₂ (Me ₃ SiC) _{p) ZrH, Ind 2 (Me} 3 Cp) ZrH, (Cp) (Ind) (MeCp) ZrH, (Cp) (Ind) (PrCp) ZrH, (Cp) (Ind) (BuCp) ZrH, (Cp) ( Ind) (Me ₂ Cp) ZrH, (Cp) (Ind) (Me ₃ SiCp) ZrH, (Cp) (Ind) (Me ₃ Cp) ZrH, MeInd ₂ (Cp) ZrH, MeInd ₂ (MeCp) ZrH, MeInd ₂ (PrCp) ZrH, MeInd ₂ (BuCp) ZrH, MeInd ₂ (Me ₂ Cp) ZrH, MeInd ₂ (Me ₃ SiCp) ZrH, MeInd ₂ (Me ₃ Cp) ZrH, (Cp) (MeInd) (MeCp) ZH , (Cp) (MeInd) (PrCp) ZrH, (Cp) (MeInd) (BuCp) ZrH, (Cp) ( _{eInd) (Me 2 Cp) ZrH} , (Cp) (MeInd) (MePrCp) ZrH, (Cp) (MeInd) (MeBuCp) ZrH, (Cp) (MeInd) (Me 3 SiCp) ZrH, (Cp) (MeInd) (Me ₃ Cp) ZrH, PhInd ₂ (Cp) ZrH, PhInd ₂ (MeCp) ZrH, PhInd ₂ (PrCp) ZrH, PhInd ₂ (BuCp) ZrH, PhInd ₂ (Me ₂ Cp) ZrH, PhInp ₂ (ZePr) , PhInd ₂ (MeBuCp) ZrH, PhInd ₂ (Me ₃ SiCp) ZrH, PhInd ₂ (Me ₃ Cp) ZrH, (Cp) (PhInd) (MeCp) ZrH, (Cp) (PhInd) (PrCp) ZrH ) (PhInd) (BuCp) ZrH, _{Cp) (PhInd) (Me 2} Cp) ZrH, (Cp) (PhInd) (MePrCp) ZrH, (Cp) (PhInd) (MeBuCp) ZrH, (Cp) (PhInd) (Me 3 SiCp) ZrH, (Cp) _{(PhInd) (Me 3 Cp)} ZrH, Me 4 Ind 2 (Cp) ZrH, Me 4 Ind 2 (MeCp) ZrH, Me 4 Ind 2 (PrCp) ZrH, Me 4 Ind 2 (BuCp) ZrH, Me 4 Ind 2 _{(Me 2 Cp) ZrH, Me} 4 Ind 2 (MePrCp) ZrH, Me 4 Ind 2 (MeBuCp) ZrH, Me 4 Ind 2 (Me 3 SiCp) ZrH, Me 4 Ind 2 (Me 3 Cp) ZrH, (Cp) _{(Me 4 Ind) (MeCp)} ZrH, (Cp) (Me 4 Ind) (PrCp) Zr _{, (Cp) (Me 4 Ind} ) (BuCp) ZrH, (Cp) (Me 4 Ind) (Me 2 Cp) ZrH, (Cp) (Me 4 Ind) (MePrCp) ZrH, (Cp) (Me 4 Ind) _{(MeBuCp) ZrH, (Cp)} (Me 4 Ind) (Me 3 SiCp) ZrH, (Cp) (Me 4 Ind) (Me 3 Cp) ZrH, BenzInd 2 (Cp) ZrH, BenzInd 2 (MeCp) ZrH, BenzInd _{2 (PrCp) ZrH, BenzInd 2} (BuCp) ZrH, BenzInd 2 (Me 2 Cp) ZrH, BenzInd 2 (MePrCp) ZrH, BenzInd 2 (MeBuCp) ZrH, BenzInd 2 (Me 3 SiCp) ZrH, BenzInd 2 (Me 3 Cp) ZrH, (Cp) (Ben) zInd) (MeCp) ZrH, (Cp) (BenzInd) (PrCp) ZrH, (Cp) (BenzInd) (BuCp) ZrH, (Cp) (BenzInd) (Me ₂ Cp) ZrH, (Cp) (BenzInd) (MePrCp) _{) ZrH, (Cp) (BenzInd} ) (MeBuCp) ZrH, (Cp) (BenzInd) (Me 3 SiCp) ZrH, (Cp) (BenzInd) (Me 3 Cp) ZrH, DibenzoInd 2 (Cp) ZrH, DibenzoInd 2 ( _{MeCp) ZrH, DibenzoInd 2 (PrCp} ) ZrH, DibenzoInd 2 (BuCp) ZrH, DibenzoInd 2 (Me 2 Cp) ZrH, DibenzoInd 2 (MePrCp) ZrH, DibenzoInd 2 (Me (BuCp) ZrH, DibenzoInd ₂ (Me ₃ SiCp) ZrH, DibenzoInd ₂ (Me ₃ Cp) ZrH, (Cp) (DibenzoInd) (MeCp) ZrH, (Cp) (DibenzoInd) (PrCp) (PrCp) _{(BuCp) ZrH, (Cp)} (DibenzoInd) (Me 2 Cp) ZrH, (Cp) (DibenzoInd) (MePrCp) ZrH, (Cp) (DibenzoInd) (MeBuCp) ZrH, (Cp) (DibenzoInd) (Me 3 SiCp ) ZrH, (Cp) (DibenzoInd) (Me ₃ Cp) ZrH, Ind ₃ ZrH, Ind ₂ (MeInd) ZrH, Ind ₂ (EtInd) ZrH, Ind ₂ (PrInd) ZrH, I _{nd 2 (BuInd) ZrH, Ind} 2 (Me 3 SiInd) ZrH, Ind 2 (Me 2 Ind) ZrH, Ind 2 (Et 2 Ind) ZrH, Ind 2 (Pr 2 Ind) ZrH, Ind 2 (Bu 2 Ind) _{ZrH, Ind 2 (Me 4 Ind} ) ZrH, Ind 2 (Et 4 Ind) ZrH, Ind 2 (Pr 4 Ind) ZrH, Ind 2 (Bu 4 Ind) ZrH, Ind 2 (NaphInd) ZrH, Ind 2 (BiPhInd) _{ZrH, (MeInd) 3 ZrH,} (EtInd) 3 ZrH, (PrInd) 3 ZrH, (BuInd) 3 ZrH, (Me 3 SiInd) 3 ZrH, (PhInd) 3 ZrH, (NaphInd) 3 ZrH, (BiPhInd) 3 ZrH, (Me ₂ Ind) ₃ ZrH, (E _{t 2 Ind) 3 ZrH, (} Pr 2 Ind) 3 ZrH, (Bu 2 Ind) 3 ZrH, (Me 2 Ind) 2 (Ind) ZrH, (Et 2 Ind) 2 (Ind) ZrH, (Pr 2 Ind) _{2 (Ind) ZrH, (Bu} 2 Ind) 2 (Ind) ZrH, (Ph 2 Ind) 2 (Ind) ZrH, (Me 3 Ind) 3 ZrH, (Et 3 Ind) 3 ZrH, (Pr 3 Ind) 3 _{ZrH, (Bu 3 Ind) 3} ZrH, (Me 4 Ind) 3 ZrH, (Et 4 Ind) 3 ZrH, (Pr 4 Ind) 3 ZrH, (Bu 4 Ind) 3 ZrH, (BenzInd) 3 ZrH, (BenzInd _{) 2 (Ind) ZrH, (} DibenzoInd) 2 (Ind) ZrH, (DibenzoInd) 3 ZrH, and the like raised .

Among the specific compounds exemplified above, those particularly preferred as catalyst components for olefin polymerization are shown below.
_{Cp 2 (MeCp) ZrH, Cp} 2 (PrCp) ZrH, Cp 2 (BuCp) ZrH, Cp 2 (Me 2 Cp) ZrH, Cp 2 (Me 3 SiCp) ZrH, Cp 2 (Me 3 Cp) ZrH, (MeCp ) ₂ (Cp) ZrH, (MeCp) ₂ (PrCp) ZrH, (MeCp) ₂ (BuCp) ZrH, (MeCp) ₂ (Me ₂ Cp) ZrH, (MeCp) ₂ (Me ₃ SiCp) ZrH, (BuCp) ₂ (Cp) ZrH, (BuCp) ₂ (MeCp) ZrH, (BuCp) ₂ (PrCp) ZrH, (BuCp) ₂ (Me ₂ Cp) ZrH, (BuCp) ₂ (Me ₃ SiCp) ZrH, (Me ₃ SiCp) _{) 2 (Cp) ZrH, (} Me 3 SiCp) 2 (MeCp) ZrH, (Me 3 SiCp) 2 (Me 2 Cp) Z _{H, (Me 3 SiCp) 2} (Me 3 Cp) ZrH, (Me 2 Cp) 2 (Cp) ZrH, (Me 2 Cp) 2 (MeCp) ZrH, (Me 2 Cp) 2 (MePrCp) ZrH, (Me _{2 Cp) 2 (MeBuCp) ZrH} , (Me 2 Cp) 2 (Me 3 Cp) ZrH, (Me 3 Cp) 2 (Cp) ZrH, (MeCp) 3 ZrH, (PrCp) 3 ZrH, (BuCp) 3 ZrH , (Me ₃ SiCp) ₃ ZrH, (Me ₂ Cp) ₃ ZrH, (Me ₃ Cp) ₃ ZrH, Ind ₂ (Cp) ZrH, Ind ₂ (MeCp) ZrH, Ind ₂ (PrCp) ZrH, Ind ₂ (BuCp) ) ZrH, Ind ₂ (Me ₂ Cp) ZrH, Ind ₂ (MePrCp) ZrH, Ind ₂ (MeBuCp) ZrH, Ind ₂ (M _{e 3 SiCp) ZrH, Ind 2} (Me 3 Cp) ZrH, BenzInd 2 (Cp) ZrH, BenzInd 2 (MeCp) ZrH, BenzInd 2 (PrCp) ZrH, BenzInd 2 (BuCp) ZrH, BenzInd 2 (Me 2 Cp) _{ZrH, BenzInd 2 (MePrCp) ZrH} , BenzInd 2 (MeBuCp) ZrH, BenzInd 2 (Me 3 SiCp) ZrH, BenzInd 2 (Me 3 Cp) ZrH, Ind 3 ZrH, Ind 2 (Me 2 Ind) ZrH, Ind 2 ( _{Et 2 Ind) ZrH, Ind 2} (Pr 2 Ind) ZrH, Ind 2 (Bu 2 Ind) ZrH, Ind 2 (Me 4 Ind) ZrH, Ind 2 (Et 4 Ind) ZrH, Ind 2 (Pr 4 Ind) Zr _{, Ind 2 (Bu 4 Ind)} ZrH, Ind 2 (NaphInd) ZrH, Ind 2 (BiPhInd) ZrH, (PhInd) 3 ZrH, (NaphInd) 3 ZrH, (BiPhInd) 3 ZrH, (Me 2 Ind) 3 ZrH, _{(Et 2 Ind) 3 ZrH,} (Pr 2 Ind) 3 ZrH, (Bu 2 Ind) 3 ZrH, (Me 4 Ind) 3 ZrH, (Et 4 Ind) 3 ZrH, (Pr 4 Ind) 3 ZrH, (Bu ₄ Ind) ₃ ZrH, (BenzInd) ₃ ZrH, (BenzInd) ₂ (Ind) ZrH, (DibenzoInd) ₃ ZrH, and the like.

Specific examples of the transition metal compound represented by the general formula (5) in the present invention are shown below.
_{That, Ind 3 ZrH, Ind 2 (} MeInd) ZrH, Ind 2 (EtInd) ZrH, Ind 2 (PrInd) ZrH, Ind 2 (BuInd) ZrH, Ind 2 (Me 3 SiInd) ZrH, Ind 2 (Me 2 Ind) _{ZrH, Ind 2 (Et 2 Ind} ) ZrH, Ind 2 (Pr 2 Ind) ZrH, Ind 2 (Bu 2 Ind) ZrH, Ind 2 (Me 4 Ind) ZrH, Ind 2 (Et 4 Ind) ZrH, Ind 2 ( _{Pr 4 Ind) ZrH, Ind 2} (Bu 4 Ind) ZrH, Ind 2 (NaphInd) ZrH, Ind 2 (BiPhInd) ZrH, (MeInd) 3 ZrH, (EtInd) 3 ZrH, (PrInd) 3 ZrH, (BuInd) _{3 ZrH, (Me 3 SiInd)} 3 _{rH, (PhInd) 3 ZrH,} (NaphInd) 3 ZrH, (BiPhInd) 3 ZrH, (Me 2 Ind) 3 ZrH, (Et 2 Ind) 3 ZrH, (Pr 2 Ind) 3 ZrH, (Bu 2 Ind) 3 _{ZrH, (Me 2 Ind) 2} (Ind) ZrH, (Et 2 Ind) 2 (Ind) ZrH, (Pr 2 Ind) 2 (Ind) ZrH, (Bu 2 Ind) 2 (Ind) ZrH, (Ph 2 Ind ) ₂ (Ind) ZrH, (Me ₃ Ind) ₃ ZrH, (Et ₃ Ind) ₃ ZrH, (Pr ₃ Ind) ₃ ZrH, (Bu ₃ Ind) ₃ ZrH, (Me ₄ Ind) ₃ ZrH, (Et _{4) Ind) 3 ZrH, (Pr 4} Ind) 3 ZrH, (Bu 4 Ind) 3 ZrH, (BenzInd) 3 ZrH, (Ben _{Ind) 2 (Ind) ZrH,} (BenzInd) (Ind) 2 ZrH, (DibenzoInd) 2 (Ind) ZrH, (DibenzoInd) (Ind) 2 ZrH, (DibenzoInd) 3 ZrH, (BenzInd) 2 (DibenzoInd) ZrH, (BenzInd) (DibenzoInd) ₂ ZrH, and (DibenzoInd) (BenzInd) (Ind) ZrH.
Here, the abbreviations in the above structural formula are as already shown.
When these compounds are used as catalyst components for olefin polymerization, two or more of these compounds can be used.

Among the specific compounds exemplified above, particularly preferable ones as catalyst components for olefin polymerization are shown below.
_{That, Ind 3 ZrH, Ind 2 (} Me 2 Ind) ZrH, Ind 2 (Et 2 Ind) ZrH, Ind 2 (Pr 2 Ind) ZrH, Ind 2 (Bu 2 Ind) ZrH, Ind 2 (Me 4 Ind) ZrH _{, Ind 2 (Et 4 Ind)} ZrH, Ind 2 (Pr 4 Ind) ZrH, Ind 2 (Bu 4 Ind) ZrH, Ind 2 (NaphInd) ZrH, Ind 2 (BiPhInd) ZrH, (PhInd) 3 ZrH, (NaphInd ) ₃ ZrH, (BiPhInd) ₃ ZrH, (Me ₂ Ind) ₃ ZrH, (Et ₂ Ind) ₃ ZrH, (Pr ₂ Ind) ₃ ZrH, (Bu ₂ Ind) ₃ ZrH, (Me ₄ Ind) ₃ Zr (Et ₄ Ind) ₃ ZrH, (Pr ₄ Ind) ₃ ZrH, (Bu _{4 Ind) 3 ZrH, (BenzInd} ) 3 ZrH, (BenzInd) (Ind) 2 ZrH, (DibenzoInd) 2 (Ind) ZrH, (DibenzoInd) (Ind) 2 ZrH, (DibenzoInd) 3 ZrH, (BenzInd) 2 ( (DibenzoInd) ZrH, (BenzInd) (DibenzoInd) ₂ ZrH, and (DibenzoInd) (BenzInd) (Ind) ZrH.

Among the specific compounds of the present invention, those particularly preferred as the catalyst component for olefin polymerization are shown below.
_{Ind 3 ZrH, (MeCp) (} Cp) 2 ZrH, (Me 3 SiCp) (Cp) 2 ZrH, (Me 3 SiCp) 3 ZrH, (MeCp) 3 ZrH, (1,3-Me 2 Cp) 3 ZrH, _{ind (1,3-Me 2 Cp)} 2 ZrH, (1-Me-3-PrCp) 3 ZrH, (BenzInd) 3 ZrH, include _(DibenzoInd) 3 ZrH like.

Synthetic examples of the novel transition metal compound of the present invention are shown below as Synthetic Methods 1 and 2, but are not limited to these synthetic methods.
<Synthesis method 1>
1) It is prepared by bringing the following compounds a), b) and c) into contact with each other.
_{^{a) (C 5 R 77 R}} 78 R 79 R 80 R 81) (C 5 R 82 R 83 R 84 R 85 R 86) M 7 X 1 2
_{^{b) C 5 HR 87 R 88}} R 89 R 90 R 91
c) LiR ⁹²
Here, C ₅ R ⁷⁷ R ⁷⁸ R ⁷⁹ R ⁸⁰ R ⁸¹ and C ₅ R ⁸² R ⁸³ R ⁸⁴ R ⁸⁵ R ⁸⁶ each represent a cyclopentadienyl group or a substituted cyclopentadienyl group in the formula, _{^{C 5 HR 87 R 88 R 89}} R 90 R 91 is cyclopentadiene or a substituted cyclopentadiene. ^{R 77, R 78, R 79} , R 80, R 81, R 82, R 83, R 84, R 85, R 86, R 87, R 88, R 49, R 50, R 91 is the formula (1 ), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹² in the novel transition metal compound of the present invention ¹³ , R ¹⁴ and R ¹⁵ are the same. X ¹ represents fluorine, chlorine, bromine, or iodine. Two X ¹ may be the same or different. Preferably it is chlorine or bromine, particularly preferably chlorine. R ⁹² represents an alkyl group such as an ethyl group, a propyl group, a butyl group, and a hexyl group. These may have branches. Preferably it is an n-butyl group.

When the compounds a), b) and c) are brought into contact, usually in an inert atmosphere such as nitrogen or argon, generally aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, cyclohexane The reaction is carried out with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon, or an oxygen-containing hydrocarbon solvent such as diethyl ether or tetrahydrofuran.
The order of contact is not particularly limited, and specifically, it is desirable to perform the contact in the following order.
After contacting compounds a) and c), b) is contacted.
Upon contact, each component may be added at once, may be added over a certain period of time, or may be added in portions. The contact of each component may be performed a plurality of times.
The contact between the compounds a) and c) is carried out usually at a temperature of -100 to 0C, preferably -80 to -40C, for 5 minutes to 24 hours, preferably 30 minutes to 3 hours. Thereafter, the temperature is raised to -30 ° C to 30 ° C, preferably around 0 ° C to 10 ° C, and the resulting alkali metal halide such as LiCl is removed by filtration. Further, after contacting the compound b), the mixture is stirred at a temperature of 0 ° C to 150 ° C, preferably 20 ° C to 80 ° C for 5 minutes to 3 days, preferably 1 hour to 24 hours. After removing the solvent in the reaction solution and washing with an aliphatic hydrocarbon such as pentane or hexane, the novel transition metal compound of the present invention can be obtained.
After the compounds a), b) and c) are brought into contact with each other and heated and stirred, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and aliphatic or alicyclic hydrocarbons such as heptane, hexane, decane, dodecane and cyclohexane are used. LiCl can also be removed from the reaction solution by filtering from a liquid inert hydrocarbon solution such as Alternatively, after removing the solvent from the reaction solution, the reaction solution may be washed with an oxygen-containing hydrocarbon solvent such as tetrahydrofuran to remove LiCl.
Compounds a) to c) are used in a proportion of 1 to 50 mol, preferably 2 to 8 mol, of compound b) and usually 2 mol of compound c) per mol of compound a). Can be.

<Synthesis method 2>
1) It is prepared by bringing the following compounds d) and e) into contact with each other.
d) Ind ₃ ZrH
^{_{e) C 5 HR 93 R 94}} R 95 R 96 R 97
^{_{Here, C 5 HR 93 R 94 R}} 95 R 96 R 97 is cyclopentadiene or a substituted cyclopentadiene. R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , in the novel transition metal compound of the present invention represented by the general formula (1). The same as R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ .
When the compounds d) and e) are brought into contact with each other, an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene, and a fat such as heptane, hexane, decane, dodecane and cyclohexane are generally used in an inert atmosphere such as nitrogen or argon. The reaction is carried out with or without stirring in the presence of a liquid inert hydrocarbon such as an aromatic or alicyclic hydrocarbon, or an oxygen-containing hydrocarbon solvent such as diethyl ether or tetrahydrofuran.
The contact between the compounds d) and e) is usually carried out at a temperature of -80 to 150 ° C, preferably 0 to 50 ° C, for 1 minute to 3 hours, preferably 10 minutes to 1 hour. Thereafter, the temperature is raised to 0 ° C to 150 ° C, preferably around 20 ° C to 110 ° C, and the mixture is stirred for 5 minutes to 3 days, preferably for 1 hour to 24 hours. After removing the solvent in the reaction solution, washing with an aliphatic hydrocarbon such as pentane or hexane, a novel transition metal compound (1) can be obtained.
With respect to the use ratio of the compounds d) and e), the compound e) can be used in a proportion of 1 to 50 mol, preferably 2 to 8 mol, per 1 mol of the compound d).
Ind ₃ ZrH of the compound d) can be obtained by the above-mentioned synthesis method 1.

  The novel transition metal compound proposed by the present invention is an organoaluminum oxy compound shown below, a compound which reacts with the novel transition metal compound to form an ion pair, and a catalyst for olefin polymerization in combination with a mixture thereof. Can be used as

The organic aluminum oxy compound has an Al-O-Al bond in the molecule, and the number of bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminum oxy compound is usually a product obtained by reacting an organoaluminum compound with water. The reaction between the organoaluminum and water is usually performed in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.
As the organoaluminum compound used for preparing the organoaluminum oxy compound, any of the compounds represented by the following general formula (7) can be used, but trialkylaluminum is preferably used.
^{_{R 98 t AlX 2 3-t}} ··· formula (7)
(Wherein, R ⁹⁸ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having 1 to 18 carbon atoms, and preferably 1 to 12 carbon atoms; X ² represents a hydrogen atom or a halogen atom; It represents an integer of ≦ t ≦ 3.)
The alkyl group of the trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group. Is particularly preferred.

The above-mentioned organoaluminum compounds may be used as a mixture of two or more.
The reaction ratio between water and the organoaluminum compound (molar ratio of water / Al) is preferably 0.25 / 1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is It is usually in the range of -70 to 100C, preferably -20 to 20C. The reaction time is selected in the range of usually 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate or the like, or a component capable of producing water in the reaction system can be used.
Among the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, and especially methylaluminoxanes (including those substantially consisting of methylaluminoxane (MAO)) And organic aluminum oxy compounds.
Of course, as the organoaluminum oxy compound, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination. You may use what was done.

In addition, specific examples of the compound that forms an ion pair by reacting with a novel transition metal compound include a borane compound and a borate compound.
More specifically, the borane compound can be represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris (p -Fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris ( 3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris (per Fluoroanthryl) borane, tris (perfluorobinaphthyl) Borane.
Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro Biphenyl) borane, tris (perfluoroanthryl) borane and tris (perfluorobinaphthyl) borane are more preferable, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane and tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified.

A specific example of a borate compound is a compound represented by the following general formula (8).
^{[L 1 -H] + [BR} 99 R 100 X 3 X 4] -
... Equation (8)
In the formula, L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, and phosphonium. Examples of the ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of the anilium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, and N, N-2,4,6-pentamethylanilinium. Examples of the phosphonium include triarylphosphonium such as triphenylphosphonium, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium, and trialkylphosphonium.
R ⁹⁹ and R ¹⁰⁰ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, which may be linked to each other by a bridging group, As the substituent of the hydrocarbon group, an alkyl group represented by a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, and a halogen such as fluorine, chlorine, bromine and iodine are preferable.
X ³ and X ⁴ are a hydride group, a halide group, a hydrocarbyl group containing 1 to 20 carbon atoms, and a substituted hydrocarbyl group containing 1 to 20 carbon atoms in which one or more hydrogen atoms have been replaced by halogen atoms.

  Specific examples of the compound represented by the general formula (8) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, and tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6- Ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (2,6-difluorophenyl) borate Dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-ditri Fluoromethylphenyl) borate, triphenylphosphoniumtetra (2,6-difluorophenyl) borate, triphenylphosphoniumtetra (perfluoronaphthyl) borate, trimethylammoniumtetra (2,6-ditrifluoromethylphenyl) borate, triethylammoniumtetra ( Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1-propyl) ) Ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenyl borate, and the like.

  Among them, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoronaphthyl) ) Borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (Perfluoronaphthyl) borate is particularly preferred.

A second example of the borate compound is represented by the following general formula (9).
^{[L 2] + [BR 101} R 102 X 5 X 6] -
... Equation (9)
In the formula, L ² is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton, etc. No. R ¹⁰¹ , R ¹⁰² , X ⁵ and X ⁶ have the same definitions as R ⁹⁹ , R ¹⁰⁰ , X ³ and X ^{4 in} the formula (8).

Specific examples of the above compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) borate G, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3.5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , NaB (o- _{F-Ph) 4, NaB (} p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) 4, NaB ( _{2,6- (CF 3) 2 -Ph)} 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H + BPh 4 - · 2 diethyl ether, H _{^{+ B (3,5-F 2 -Ph}} ) 4 · 2 diethyl ^{_{ether, H + B (C 6 F}} 5) 4 - · 2 diethyl _{^{ether, H + B (2,6- (CF}} 3) 2 -Ph) _4-2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ether ^can be exemplified by _{H + B (C 10 H 7} ) 4 · 2 diethyl ether.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropi Tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, NaB _{(C 6 F 5) 4,} NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, H ^{_{+ B (C 6 F 5)}} 4 - · 2 diethyl ether, ^{_{+ B (2,6- (CF 3)}} 2 -Ph) 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^ether, H + B _{(C 10} H _{7) 4-2} diethyl ether.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) methylphenyl) _{borate, NaB (C 6 F 5)} 4, NaB (2,6- (CF 3) 2 -Ph) 4, H + B (C 6 F 5) 4 - · 2 diethyl ^{ether, H} + B ( _{2,6- (CF 3) 2 -Ph)} 4 · 2 diethyl _{^{ether, H + B (3,5- (CF}} 3) 2 -Ph) 4 · 2 diethyl ^{_{ether, H + B (C 10 H}} 7) 4 2 diethyl ether.

An olefin polymerization catalyst comprising the novel transition metal compound of the present invention, an organoaluminum oxy compound, a compound that reacts with the novel transition metal compound to form an ion pair, or a mixture thereof is supported on a carrier to form a solid catalyst. Can be used as
As the carrier, an inorganic carrier, a particulate polymer carrier or a mixture thereof is used. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbon material, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.
Examples of the metal oxide include single oxides and multiple oxides of elements of the periodic table groups 1 to 14, for example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , and ZrO. ₂ , Fe ₂ O ₃ , Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, Al ₂ O ₃ .SiO ₂ , Al ₂ O ₃ .MgO.CaO, Al ₂ O ₃ .MgO.SiO ₂ , Al ₂ Various natural or synthetic multiple oxides such as O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO can be exemplified. Here, the above formula is not a molecular formula, but only a composition, and the structure and component ratio of the double oxide used in the present invention are not particularly limited.
In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.
As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable.
The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon. Although any of the above inorganic carriers can be suitably used in the present invention, it is particularly preferable to use metal oxides, silica, alumina and the like.

These inorganic carriers are usually calcined at 200 to 800 ° C., preferably 400 to 600 ° C. in air or an inert gas such as nitrogen or argon to adjust the amount of surface hydroxyl groups to 0.8 to 1.5 mmol / g. It is preferable to use them.
The properties of these inorganic carriers are not particularly limited, but usually have an average particle size of 5 to 200 μm, preferably 10 to 150 μm, a specific surface area of 150 to 1000 m ² / g, preferably 200 to 500 m ² / g, and a pore volume. the 0.3~2.5cm ³ / g, preferably 0.5~2.0cm ³ / g, apparent specific gravity is 0.20~0.50g / cm ^3, preferably 0.25～0.45G / It is preferable to use an inorganic carrier having cm ³ .
The above-mentioned inorganic carriers can of course be used as they are, but as a pretreatment, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, diisobutylaluminum. It can be used after being brought into contact with an organic aluminum compound such as aluminum hydride or an organic aluminum oxy compound containing an Al-O-Al bond.

Contact between the novel transition metal compound of the present invention, an organoaluminum oxy compound, a compound that reacts with the novel transition metal compound to form an ion pair, or a mixture thereof, and each component when an olefin polymerization catalyst is obtained from a carrier The method is not particularly limited, and for example, the following method can be arbitrarily adopted.
(I) A novel transition metal compound, an organoaluminum oxy compound, and a compound that reacts with the novel transition metal compound to form an ion pair are contacted, and then contacted with a carrier.
(II) After bringing the novel transition metal compound into contact with the carrier, the organoaluminum oxy compound is brought into contact with a compound which reacts with the novel transition metal compound to form an ion pair.
(III) The organic aluminum oxy compound, a compound that reacts with the novel transition metal compound to form an ion pair, is brought into contact with the carrier, and then contacted with the novel transition metal compound.
Among these contact methods, (I) and (III) are particularly preferred. In any of the contact methods, usually, in an inert atmosphere such as nitrogen or argon, generally, an aromatic hydrocarbon (typically having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane And a method of contacting each component with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (generally having 5 to 12 carbon atoms) such as cyclohexane.
This contact is carried out at a temperature of usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C for 10 minutes to 50 hours, preferably 1 hour to 24 hours.
When the carrier is brought into contact with a new transition metal compound, an organoaluminum oxy compound, or a compound that reacts with the new transition metal compound to form an ion pair, as described above, certain components are soluble or hardly soluble. Both aromatic hydrocarbon solvents and aliphatic or alicyclic hydrocarbon solvents in which certain components are insoluble or hardly soluble can be used.
When the contact reaction between the components is performed stepwise, the solvent used in the former step may be used as it is as the solvent for the subsequent contact reaction without removing the solvent used in the former step. In addition, after the previous contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or hardly soluble (for example, aliphatic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene) Hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons) to recover the desired product as a solid, or once remove some or all of the soluble solvent by drying or other means to obtain the desired product. After removal of the product as a solid, a subsequent catalytic reaction of the desired product can also be performed using any of the inert hydrocarbon solvents described above. The present invention does not prevent the contact reaction of each component from being performed a plurality of times.

The novel transition metal compound and the organoaluminum oxy compound of the present invention, the novel transition metal compound, and the compound that reacts with the novel transition metal compound to form an ion pair, the use ratio of the carrier is not particularly limited, but Is preferable.
When an organic aluminum oxy compound is used, the atomic ratio (Al / M) of aluminum of the organic aluminum oxy compound to the transition metal (M) in the novel transition metal compound is usually 1 to 100,000, preferably 5 to 1000. When a compound that reacts with the novel transition metal compound to form an ion pair is used, the atomic ratio of boron to the transition metal of the novel transition metal compound (B / M) is preferably selected in the range of usually 0.01 to 100 mol, preferably 0.1 to 50 mol, more preferably 0.2 to 10 mol.
The support is used in an amount of 1 g per 0.0001 to 5 mmol of the transition metal in the novel transition metal compound, preferably per 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol. is there.
The novel transition metal compound, the organoaluminum oxy compound, the compound that reacts with the novel transition metal compound to form an ion pair and the carrier are contacted with each other by any one of the contact methods (I) to (III). Thereafter, by removing the solvent, the olefin polymerization catalyst can be obtained as a solid catalyst. The removal of the solvent is performed at normal pressure or reduced pressure at 0 to 200 ° C, preferably 20 to 150 ° C, for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

The olefin polymerization catalyst can also be obtained by the following method.
(IV) The solvent is removed by contacting the novel transition metal compound with a carrier, and this is used as a solid catalyst component, and under polymerization conditions, an organoaluminum oxy compound, reacting with the novel transition metal compound to form an ion pair. With the compound to be prepared.
(V) an organoaluminum oxy compound, a compound that forms an ion pair by reacting with the novel transition metal compound and the carrier are brought into contact with each other to remove the solvent, and this is used as a solid catalyst component. Make contact.
In the case of the contact methods (IV) and (V), the same conditions as those described above can be used for the component ratio, the contact condition, and the solvent removal condition.

Further, the novel transition metal compound of the present invention can be used as a catalyst by being supported on a layered silicate.
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force.
Most layered silicates occur naturally mainly as a main component of clay minerals, but these layered silicates are not particularly limited to those naturally occurring, and may be artificially synthesized.
Among these, smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, vermiculite, and mica are preferred.
In general, natural products are often non-ion-exchangeable (non-swellable). In such a case, in order to have a preferable ion-exchangeability (or swellability), the natural product must have ion-exchangeability (or swellability). It is preferable to perform a process for applying. Among such treatments, particularly preferred are the following chemical treatments. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used. Specifically, (a) acid treatment using hydrochloric acid, sulfuric acid, or the like, (b) alkali treatment using NaOH, KOH, NH _3, or the like; A salt treatment using a salt comprising at least one selected from the group consisting of a cation containing at least one selected atom and a halogen atom or an anion derived from an inorganic acid; (d) alcohol, carbonization Treatment with an organic substance such as a hydrogen compound, formamide, and aniline is exemplified. These processes may be performed independently, or two or more processes may be combined.

  The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, sorting, etc. at any time before, during, or after all the steps. The method can be any suitable one. In particular, for the granulation method, for example, spray granulation method, tumbling granulation method, compression granulation method, stirring granulation method, briquetting method, compacting method, extrusion granulation method, fluidized bed granulation method, An emulsion granulation method and a submerged granulation method are exemplified. Particularly preferred granulation methods are spray granulation method, tumbling granulation method and compression granulation method.

  The above-mentioned layered silicates can of course be used as they are, but these layered silicates can be used as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, diisobutyl aluminum It can be used in combination with an organic aluminum compound such as aluminum hydride or an organic aluminum oxy compound containing an Al—O—Al bond.

In order to support the novel transition metal compound of the present invention on the layered silicate, the transition metal compound and the layered silicate are brought into contact with each other, or the transition metal compound, the organoaluminum compound, and the layered silicate are brought into contact with each other. Good. The method of contacting each component is not particularly limited, and for example, the following method can be arbitrarily adopted.
(VI) The novel transition metal compound is brought into contact with the organoaluminum compound, and then brought into contact with the layered silicate carrier.
(VII) After bringing the novel transition metal compound into contact with the carrier, it is brought into contact with an organoaluminum compound.
(VIII) After bringing the organic aluminum oxy compound into contact with the carrier, it is brought into contact with the novel transition metal compound.
Among these contact methods, (I) and (III) are particularly preferred. In any of the contact methods, usually, in an inert atmosphere such as nitrogen or argon, generally, an aromatic hydrocarbon (typically having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane And a method of contacting each component with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (generally having 5 to 12 carbon atoms) such as cyclohexane.
The proportions of the novel transition metal compound, the organoaluminum compound and the carrier are not particularly limited, but the following ranges are preferred.
The supported amount of the novel transition metal compound is 0.0001 to 5 mmol, preferably 0.001 to 0.5 mmol, more preferably 0.01 to 0.1 mmol, per 1 g of the layered silicate.
When an organic aluminum compound is used, the amount of Al carried is preferably in the range of 0.01 to 100 mol, preferably 0.1 to 50 mol, and more preferably 0.2 to 10 mol.
For the method of supporting and removing the solvent, the same conditions as those for the above-mentioned inorganic carrier can be used.
The olefin polymerization catalyst thus obtained may be used after preliminarily polymerizing the monomer, if necessary.

The polymerization catalyst described above can be used for homopolymerization or copolymerization of olefins. The olefins referred to herein include α-olefins, cyclic olefins, dienes, trienes, styrene analogs, and polar group-containing olefins.
The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like. Illustrated. The α-olefins can be homopolymerized using the catalyst component of the present invention, and can also be copolymerized with two or more α-olefins. Either polymerization or block copolymerization may be used. For the copolymerization of α-olefins, ethylene and propylene, such as ethylene and 1-butene, ethylene and 1-hexene, and ethylene and 4-methyl-1-pentene, have 3 to 12 carbon atoms, preferably 3 to 12 carbon atoms. When copolymerizing α-olefins having a carbon number of 3 to 8 such as propylene and 1-butene, propylene and 4-methyl-1-pentene, propylene and 1-hexene, and propylene and 1-octene, It includes the case of copolymerizing 12, preferably 3 to 8 α-olefins. When ethylene or propylene is copolymerized with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of the total monomers. In a polymer, it is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and in a propylene copolymer, it is 1 to 90 mol%, preferably 5 to 90 mol%. %, More preferably in the range of 10 to 70 mol%.

  As the cyclic olefin, those having 3 to 24, preferably 3 to 18 carbon atoms can be used in the present invention, and examples thereof include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, and cyclodecene. , Cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like. Usually, the cyclic olefin is copolymerized with the above-mentioned α-olefin. In this case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. % Range.

  Dienes and trienes that can be used in the present invention include those having 4 to 24 carbon atoms, preferably 4 to 18 carbon atoms, and specifically, butadiene, 1,4-hexadiene, and 1,5-hexadiene. 1,1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene, , 5,9-decatriene and the like. When a chain diene or triene is used in the present invention, it is customary to copolymerize with the above-mentioned α-olefin, but the content of the chain diene and / or triene in the copolymer is generally , 0.1 to 50 mol%, preferably 0.2 to 10 mol%.

  Styrene analogs that can be used in the present invention are styrene and styrene derivatives, which include t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N , N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like.

The polymerization reaction can be performed by slurry polymerization, solution polymerization, or gas phase polymerization in the presence of the above-mentioned catalyst. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state in which oxygen, water and the like are substantially turned off, aliphatic hydrocarbons such as isobutane, hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and methyl. The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from alicyclic hydrocarbons such as cyclohexane. The polymerization conditions at this time are a temperature of 20 to 200 ° C., preferably 50 to 100 ° C., a pressure in the range of normal pressure to 7 MPa, preferably normal pressure to 3 MPa, and a polymerization time of 5 minutes to 10 hours, preferably 5 to 10 hours. Minutes to 5 hours are usually employed.
Although the molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, it is possible to more effectively control the molecular weight by adding hydrogen to the polymerization reaction system. it can.

Further, even if a component for the purpose of removing water, a so-called scavenger, is added to the polymerization system, the reaction can be carried out without any problem. Examples of such a scavenger include an organic aluminum compound such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; the above-mentioned organic aluminum oxy compound; a modified organoaluminum compound containing a branched alkyl; an organic zinc compound such as diethyl zinc and dibutyl zinc; Organic magnesium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum and ethylbutylmagnesium are preferred, and triethylaluminum is particularly preferred.
The present invention can be applied to a two-stage or more multi-stage polymerization system in which polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, and polymerization temperature are different from each other.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods.
<Measurement of melting point by differential scanning calorimeter (DSC)>
Using a DSC6200R melting point apparatus manufactured by Seiko Denshi, a sample (5 mg) was kept at 180 ° C. for 3 minutes, then cooled at 10 ° C./min to 0 ° C., kept at 0 ° C. for 10 minutes, and then kept at 10 ° C./min. The melting point was measured by raising the temperature in minutes.
<Measurement of molecular weight and molecular weight distribution by GPC>
Waters
The molecular weight distribution was determined using alliance GPC 2000 under the conditions of column showdex HT-806M, solvent 1,2,4-trichlorobenzene, temperature 140 ° C., flow rate 1.0 ml / min.
<Melt index (MI)>
ASTM D 1238-57T Measured at 190 ° C under a load of 2.16 kg.

<Example 1>
Under a nitrogen atmosphere, 1 mmol (0.39 g) of bisindenyl zirconium dichloride (Ind ₂ ZrCl ₂ ) was suspended in 30 ml of toluene in a 100 ml eggplant-shaped flask, cooled to -78 ° C. with a cryogen (dry ice-ethanol), and n 2 mmol of -butyllithium (n-BuLi) are added. The mixed solution is taken out of the cryogen, the temperature is slowly raised, and around 0 ° C., 4 mmol of indene is added. The temperature is further raised to room temperature and the reaction is carried out for 30 minutes. After the reaction, the precipitated lithium chloride (LiCl) is filtered off. The filtrate was further reacted at 50 ° C. for 12 hours, and the deposited precipitate was washed with n-hexane to obtain Ind ₃ ZrH at a yield of 64%. The structure of this compound was determined by ¹ H-NMR, ¹³ C-NMR and X-ray structure analysis.
Typical NMR peak
¹ H-NMR (THF-d ₈ , Me ₄ Si): δ 2.03 (t, 3H), 2.95 (s, 1H), 5.79 (br, 6H), 6.97 (m, 6H) , 7.34 (m, 6H); ¹³ C-NMR (THF-d ₈ , Me ₄ Si) δ 90.12, 115.77, 123.51, 124.37, 131.36.
FIG. 1 shows the structure obtained by computer processing based on the X-ray diffraction data of the compound obtained in Example 1.

<Example 2>
Under a nitrogen atmosphere, 1 mmol (0.29 g) of biscyclopentadienyl zirconium dichloride (Cp ₂ ZrCl ₂ ) was dissolved in 30 ml of toluene in a 100 ml eggplant-shaped flask, and cooled to −78 ° C. with a cryogen (dry ice-ethanol). , 2 mmol of n-butyllithium (n-BuLi). The mixed solution is taken out of the cryogen, the temperature is slowly raised, and around 0 ° C., 4 mmol of methylcyclopentadiene is added. The temperature is further raised to room temperature and the reaction is carried out for 30 minutes. After the reaction, the precipitated lithium chloride (LiCl) is filtered off. The filtrate was further reacted at 50 ° C. for 12 hours, and after removing the solvent, the precipitated solid was washed with n-hexane to obtain (MeCp) (Cp) ₂ ZrH in a yield of 70%. The structure of this compound was determined by ¹ H-NMR and ¹³ C-NMR.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 2.17 (s, 3H), 2.98 (s, 1H), 4.79 (t, 2H), 5.31 (t, 2H) , 5.34 (s, 10H); ¹³ C-NMR (C ₆ D ₆ , Me ₄ Si) δ 16.38, 102.55, 105.43, 110.04, 118.50

<Example 3>
Under a nitrogen atmosphere, 1 mmol (0.29 g) of biscyclopentadienyl zirconium dichloride (Cp ₂ ZrCl ₂ ) was dissolved in 30 ml of toluene in a 100 ml eggplant-shaped flask, and cooled to −78 ° C. with a cryogen (dry ice-ethanol). , 2 mmol of n-butyllithium (n-BuLi). The mixed solution is taken out of the cryogen, the temperature is slowly raised, and around 0 ° C., 4 mmol of trimethylsilylcyclopentadiene is added. The temperature is further raised to room temperature and the reaction is carried out for 30 minutes. After the reaction, the precipitated lithium chloride (LiCl) is filtered off. The filtrate was further reacted at 80 ° C. for 3 hours, and after removing the solvent, the precipitated solid was washed with n-hexane to obtain (Me ₃ SiCp) (Cp) ₂ ZrH at a yield of 87%. The structure of this compound was determined by ¹ H-NMR.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 0.40 (s, 9H), 2.65 (s, 1H), 4.48 (t, 2H), 5.29 (s, 10H) , 5.67 (t, 2H)

<Example 4>
Under a nitrogen atmosphere, 1 mmol (0.44 g) of the trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 is suspended in 30 ml of toluene, and 8 mmol of trimethylsilylcyclopentadiene is added to a 100 ml eggplant-shaped flask. After reacting at 80 ° C. for 3 hours and removing the solvent, the precipitated solid was washed with n-hexane to obtain (Me ₃ SiCp) ₃ ZrH in a yield of 88%. The structure of this compound was determined by ¹ H-NMR and ¹³ C-NMR.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 3.35 (s, 1 H), 4.83 (t, 6 H), 5.86 (t, 6 H); ¹³ C-NMR (C ₆ D ₆ , Me ₄ Si) δ 106.28, 110.10, 116.08

<Example 5>
Under a nitrogen atmosphere, 1 mmol (0.44 g) of the trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 is suspended in 30 ml of toluene, and 8 mmol of methylcyclopentadiene is added to a 100 ml eggplant-shaped flask. After reacting at 80 ° C. for 3 hours and removing the solvent, the precipitated solid was washed with n-hexane to obtain (MeCp) ₃ ZrH in a yield of 87%. The structure of this compound was determined by ¹ H-NMR and ¹³ C-NMR.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 2.68 (s, 9 H), 3.25 (s, 1 H), 4.85 (t, 6 H), 5.40 (t, 6 H) ¹³ C-NMR (C ₆ D ₆ , Me ₄ Si) δ 16.41, 103.19, 110.52, 119.16

<Example 6>
Under a nitrogen atmosphere, 1 mmol (0.44 g) of the trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 was suspended in 30 ml of toluene in a 100 ml eggplant-shaped flask, and 8 mmol of 1,3-dimethylcyclopentadiene was added. . After reacting at 80 ° C. for 3 hours and removing the solvent, the precipitated solid was washed with n-hexane to obtain (1,3-Me ₂ Cp) ₃ ZrH in a yield of 80%. The structure of this compound was determined by ¹ H-NMR, ¹³ C-NMR and X-ray structure analysis.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 2.25 (s, 18 H), 3.48 (s, 1 H), 4.60 (t, 3 H), 4.93 (d, 6 H) ¹³ C-NMR (C ₆ D ₆ , Me ₄ Si) δ 15.90, 108.41, 115.36, 118.00
FIG. 2 shows the structure obtained by computer processing based on the X-ray diffraction data of the compound obtained in Example 6.

<Example 7>
Under a nitrogen atmosphere, 0.42 mmol (0.185 g) of trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 was suspended in 8.4 ml of toluene in a 50 ml eggplant-shaped flask, and the mixture was suspended in 1,4-dimethylcyclohexane. 1.68 mmol of pentadiene was added and reacted at 40 ° C. for 48 hours to obtain Ind (1,3-Me ₂ Cp) ₂ ZrH. ^The yield quantified by ¹ H-NMR was 50%.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 3.56 (s, 1H), 4.23 (t, 2H), 4.42 (t, 2H), 4.57 (t, 2H)

Example 8
Under a nitrogen atmosphere, 2.9 mmol (1.27 g) of trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 was suspended in 50 ml eggplant-shaped flask in 30 ml of toluene, and the mixture was suspended in 1-methyl-3-propylcyclohexane. 11.6 mmol of pentadiene was added and reacted at 80 ° C. for 2 hours. After removal of the solvent, by washing the precipitated solid with n- hexane to give (1-Me-3-PrCp ) 3 ZrH in 90% yield. The structure of this compound was determined by ¹ H-NMR.
Typical NMR peak
^{_{1 H-NMR (C 6 D}} 6, Me 4 Si): δ0.96 (t, 9H), 2.27 (t, 9H), 3.41 (s, 1H), 4.63 (s, 3H) , 4.90 (m, 3H), 4.96 (m, 3H)

<Example 9>
Under a nitrogen atmosphere, 0.31 mmol (0.14 g) of trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 was suspended in 5 ml of hexane in a 50 ml eggplant-shaped flask, and benzoindene (BenzInd) 1.2 mmol was suspended. In addition, the reaction was performed at 50 ° C. for 2 hours. After removing the solvent, the precipitated solid was washed with n-hexane to obtain (BenzInd) ₃ ZrH in a yield of 83%. The structure of this compound was determined by ¹ H-NMR.
Typical NMR peak
¹ H-NMR (C ₆ D ₆ , Me ₄ Si): δ 3.30 (t, 3H), 3.85 (s, 1H), 5.80 (s, 3H), 5.97 (s, 3H) , 7.25 (t, 3H), 7.35 (t, 3H) 7.66 (d, 3H), 7.51 (d, 3H)

<Example 10>
Under a nitrogen atmosphere, 0.64 mmol (0.28 g) of the trisindenyl zirconium hydride (Ind ₃ ZrH) obtained in Example 1 was placed in a 50 ml eggplant-shaped flask, and 21 ml of a 0.1 mol / l toluene solution of dibenzoindene was added. In addition, the mixture was suspended and reacted at 80 ° C. for 30 minutes (a solid solution was deposited after heating to form a homogeneous solution). The precipitate was collected by filtration and washed with n-pentane to recover 0.38 g. When this solid was decomposed with methanol and analyzed by ¹ H-NMR, only dibenzoindene was confirmed. From the amount of dibenzoindene generated by the decomposition, it was found that the solid obtained by the reaction was (DibenzoInd) ₃ ZrH. (81% yield)

<Example 11>
The following polymerization reaction was carried out using the compound Ind ₃ ZrH obtained in Example 1 as a catalyst component.
5 ml of toluene was added to a 20 ml Schlenk tube purged with nitrogen, 5.0 μmol of the compound Ind ₃ ZrH was further added, and 5.0 mmol of a toluene solution of MAO (2.6 mmol / ml) was further added at room temperature and stirred for 5 minutes.
After replacing a 200 ml stainless steel autoclave equipped with a stirrer with nitrogen, 100 ml of toluene was added, 1.4 ml of the above catalyst solution was further added, and the mixture was heated to 80 ° C. with stirring. Next, ethylene was charged into the autoclave so that the pressure became 0.6 MPa, polymerization was started, and polymerization was performed for 5 minutes. The polymerization was stopped by adding ethanol.
Polyethylene was obtained by polymerization, and the polymerization activity was 74 kgPE / (mmolZr · MPa · h), Mw = 102,600, and Mw / Mn = 2.97.

<Example 12>
Using the compound Ind ₃ ZrH obtained in Example 1, the following polymerization reaction was performed.
Under a nitrogen atmosphere, 0.4 mmol of the compound Ind ₃ ZrH obtained in Example 1 was collected in a 100 ml flask, and 15 ml of toluene was added to obtain a toluene suspension. Then, 40 mmol of a methylaluminoxane solution having a concentration of 2.6 mmol / ml (the number of moles of Al atom) was added, and the mixture was stirred at room temperature for 10 minutes.
10 g of SiO ₂ calcined at 400 ° C. for 5 hours was added to a 300 ml flask, the whole amount of the above solution was added, and the solvent was removed under nitrogen blowing and reduced pressure to obtain a fluid solid catalyst component.
To a 2.7 L stainless steel autoclave equipped with a stirrer and purged with nitrogen and kept at a temperature of 75 ° C., 0.25 ml of a hexane solution (0.5 mmol / ml) of triethylaluminum and 130 mg of the above solid catalyst were added. Each gas was supplied while adjusting the 1-butene / ethylene molar ratio in the gas phase to 0.12, and polymerization was carried out for 2 hours while maintaining the total pressure at 0.9 MPa.
The activity was 1,730 g / (g catalyst · MPa · h), and the resulting ethylene copolymer had an MI of 1.4 g / 10 min, a density of 0.9248 g / cm ³ , Mw = 124,500, and Mw / Mn = 2. The bulk density was 0.42 g / cm ³ and the melting point was 118.1 ° C.

<Example 13>
Using the compound (1,3-Me ₂ Cp) ₃ ZrH obtained in Example 6, the following polymerization reaction was performed.
5 ml of toluene was added to a 20 ml Schlenk tube purged with nitrogen, 5.0 μmol of the compound (1,3-Me ₂ Cp) ₃ ZrH was further added, and 5.0 mmol of a toluene solution of MAO (2.6 mmol / ml) was further added at room temperature. The mixture was stirred for 1 minute.
After replacing a 200 ml stainless steel autoclave equipped with a stirrer with nitrogen, 100 ml of toluene was added, 1.4 ml of the above catalyst solution was further added, and the mixture was heated to 80 ° C. with stirring. Next, ethylene was charged into the autoclave so that the pressure became 0.6 MPa, polymerization was started, and polymerization was performed for 5 minutes. The polymerization was stopped by adding ethanol.
Polyethylene was obtained by polymerization, and the polymerization activity was 60 kgPE / (mmolZr · MPa · h).

<Example 14>
Using the compound (Me ₂ Cp) ₃ ZrH obtained in Example 6, the following polymerization reaction was performed.
Under a nitrogen atmosphere, 0.2 mmol of the compound (Me ₂ Cp) ₃ ZrH obtained in Example 6 was collected in a 100 ml flask, and 15 ml of toluene was added to obtain a toluene suspension. Then, 40 mmol of a methylaluminoxane solution having a concentration of 2.9 mmol / ml (the number of moles of Al atoms) was added, and the mixture was stirred at room temperature for 10 minutes.
10 g of SiO ₂ calcined at 650 ° C. for 5 hours was added to a 300 ml flask, the entire amount of the above solution was added, and the solvent was removed under nitrogen blowing and reduced pressure to obtain a fluid solid catalyst component.
To a 2.7 L stainless steel autoclave equipped with a stirrer whose inside was replaced with nitrogen and the temperature was kept at 75 ° C., 0.3 ml of a hexane solution (0.5 mmol / ml) of triethylaluminum and 70 mg of the above solid catalyst were added. The polymerization was carried out for 2 hours while supplying each gas such that the 1-butene / ethylene molar ratio in the gas phase became 0.08, the hydrogen concentration became 600 ppm, and the total pressure became 0.9 MPa.
The activity was 350 gPE / (g catalyst · MPa · h), and the produced ethylene copolymer had an MI of 0.23 g / 10 min, a density of 0.9160 g / cm ³ , Mw = 140,000, and Mw / Mn = 3. 0.4 and a bulk density of 0.38 g / cm ³ .

<Example 15>
The following polymerization reaction was carried out using the compound (BenzInd) ₃ ZrH obtained in Example 9.
Under a nitrogen atmosphere, 0.2 mmol of the compound (BenzInd) ₃ ZrH obtained in Example 9 was collected in a 100 ml flask, and 15 ml of toluene was added to obtain a toluene suspension. Then, 40 mmol of a methylaluminoxane solution having a concentration of 2.9 mmol / ml (the number of moles of Al atoms) was added, and the mixture was stirred at room temperature for 10 minutes.
10 g of SiO ₂ calcined at 650 ° C. for 5 hours was added to a 300 ml flask, the entire amount of the above solution was added, and the solvent was removed under nitrogen blowing and reduced pressure to obtain a fluid solid catalyst component.
To a 2.7 L stainless steel autoclave equipped with a stirrer whose inside was replaced with nitrogen and the temperature was kept at 75 ° C., 0.3 ml of a hexane solution (0.5 mmol / ml) of triethylaluminum and 90 mg of the above solid catalyst were added, and the autoclave was added. The polymerization was carried out for 2 hours while supplying each gas such that the 1-butene / ethylene molar ratio in the gas phase became 0.08, the hydrogen concentration became 700 ppm, and the total pressure became 0.9 MPa.
The activity was 200 gPE / (g catalyst · MPa · h), and the resulting ethylene copolymer had an MI of 0.52 g / 10 min, a density of 0.9200 g / cm ³ , Mw = 100,000, and Mw / Mn = 3. 0.2 and a bulk density of 0.39 g / cm ³ .

<Example 16>
Using the compound Ind ₃ ZrH obtained in Example 1, the following polymerization reaction was performed.
Under a nitrogen atmosphere, 0.2 mmol of the compound Ind ₃ ZrH obtained in Example 1 was collected in a 50 ml flask, and 10 ml of toluene was added to obtain a toluene suspension. Then, 8.7 ml (Al: 10 mmol) of a triisobutylaluminum solution having a concentration of 1.15 mmol / ml (molar number of Al atoms) was added, and the mixture was stirred at room temperature for 10 minutes.
10 g of the layered silicate was added to a 300 ml flask and dried in vacuum at 180 ° C., then the entire amount of the above solution was added, and the solvent was removed under nitrogen blowing and reduced pressure to obtain a fluid solid catalyst component.
900 ml of hexane, 1.0 ml of a hexane solution of triisobutylaluminum (0.1 mmol / ml) and 1.0 ml of 1-hexene were placed in a 2.7-liter stainless steel autoclave equipped with a stirrer and purged with nitrogen and maintaining the temperature at 75 ° C. And the solid catalyst was added in an amount of 130 mg, and polymerization was carried out for 2 hours while supplying ethylene so as to keep the total pressure of the autoclave at 0.9 MPa.
The activity was 1,730 g / (g catalyst · MPa · h), and the resulting ethylene copolymer had an MI of 0.9 g / 10 min, a density of 0.9269 g / cm ³ , Mw = 132,600, and Mw / Mn = 2. 0.2 and a bulk density of 0.42 g / cm ³ .

<Comparative Example 1>
The following polymerization reaction was carried out using Ind ₂ ZrCl ₂ as a catalyst component.
5 ml of toluene was added to a 20 ml Schlenk tube purged with nitrogen, 5.0 μmol of the compound Ind ₂ ZrCl ₂ was further added, and 5.0 mmol of a toluene solution of MAO (2.6 mmol / ml) was further added at room temperature, followed by stirring for 30 minutes.
After replacing a 200 ml stainless steel autoclave equipped with a stirrer with nitrogen, 100 ml of toluene was added, 1.4 ml of the above catalyst solution was further added, and the mixture was heated to 80 ° C. with stirring. Next, ethylene was charged into the autoclave so that the pressure became 0.6 MPa, polymerization was started, and polymerization was performed for 5 minutes. The polymerization was stopped by adding ethanol.
Polyethylene was obtained by polymerization, and the polymerization activity was 43 kgPE / (mmolZr · MPa · h).

<Comparative Example 2>
The following polymerization reaction was carried out using Ind ₂ ZrCl ₂ .
Under a nitrogen atmosphere, 0.4 mmol of the compound Ind ₂ ZrCl ₂ was collected in a 100 ml flask, and 15 ml of toluene was added to obtain a toluene suspension. Then, 40 mmol of a methylaluminoxane solution having a concentration of 2.6 mmol / ml (the number of moles of Al atom) was added, and the mixture was stirred at room temperature for 10 minutes.
10 g of SiO ₂ calcined at 400 ° C. for 5 hours was added to a 300 ml flask, the entire amount of the above solution was added, and the solvent was removed under nitrogen blowing and reduced pressure to obtain a fluid solid catalyst component.
To a 2.7 L stainless steel autoclave equipped with a stirrer and purged with nitrogen and kept at a temperature of 75 ° C., 0.25 ml of a hexane solution (0.5 mmol / ml) of triethylaluminum and 130 mg of the above solid catalyst were added. Each gas was supplied while adjusting the 1-butene / ethylene molar ratio in the gas phase to 0.12, and polymerization was carried out for 2 hours while maintaining the total pressure at 0.9 MPa.
Activity was 750 g / (g catalyst · MPa · h), the resulting ethylene copolymer MI is 0.4 g / 10 min, density 0.9148g / cm ^3, a bulk density of 0.38 g / cm ^3, melting point 114 0.7 ° C.

  The transition metal compound of the present invention becomes a catalyst component for olefin polymerization having excellent polymerization activity. Further, since the transition metal compound does not include a halogen element, the halogen element is not included in the olefin polymer, and therefore, the amount of the stabilizer and the like can be reduced.

FIG. 2 is a view showing a structure obtained by computer processing based on X-ray diffraction data of the compound synthesized in Example 1. FIG. 9 is a view showing a structure obtained by computer processing based on X-ray diffraction data of the compound synthesized in Example 6.

Claims (18)

A novel transition metal compound (1) having a structure represented by the following general formula (1).
_{^{(C 5 R 1 R 2 R}} 3 R 4 R 5) (C 5 R 6 R 7 R 8 R 9 R 10) (C 5 R 11 R 12 R 13 R 14 R 15) M 1 H
... Equation (1)
[Wherein, C ₅ R ¹ R ² R ³ R ⁴ R ⁵ , C ₅ R ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ and C ₅ R ¹¹ R ¹² R ¹³ R ¹⁴ R ¹⁵ each represent a cyclopentadienyl group, Alternatively, it represents a substituted cyclopentadienyl group, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or an organic silicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, and may be the same or different. Among them, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). However, at least ^one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ Is a substituent other than a hydrogen atom. M ¹ represents a transition metal of Group 4 of the periodic table. ] The transition metal compound according to claim 1, having a structure represented by the following general formula (2).
_{^{(C 5 R 16 R 17 R}} 18 R 19 R 20) (C 5 R 21 R 22 R 23 R 24 R 25) (C 5 H 2 R 26 R 27 R 28) M 2 H
... Equation (2)
[Wherein C ₅ R ¹⁶ R ¹⁷ R ¹⁸ R ¹⁹ R ²⁰ , C ₅ R ²¹ R ²² R ²³ R ²⁴ R ²⁵ , and C ₅ H ₂ R ²⁶ R ²⁷ R ²⁸ each represent a cyclopentadienyl group, or Represents a substituted cyclopentadienyl group, and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are hydrogen. An atom, a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent, which may be the same or different. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , or R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , or R ²⁶ , R ²⁷ , R ²⁸ are respectively bonded to each other to form a ring. A hydrocarbon group (including a polycyclic structure) may be formed. However, at least one of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ is a substitution other than a hydrogen atom. Group. M ² represents a periodic table group IV transition metals. ] The transition metal compound according to claim 2, wherein R ²⁶ , R ²⁷ , and R ²⁸ are bonded to carbons adjacent to the first, second, and third positions. The transition metal compound according to claim 1, having a structure represented by the following general formula (3).
_{^{(C 5 H 2 R 29 R}} 30 R 31) (C 5 H 2 R 32 R 33 R 34) (C 5 H 2 R 35 R 36 R 37) M 3 H
... Equation (3)
[Wherein (C ₅ H ₂ R ²⁹ R ³⁰ R ³¹ ), (C ₅ H ₂ R ³² R ³³ R ³⁴ ), and (C ₅ H ₂ R ³⁵ R ³⁶ R ³⁷ ) each represent cyclopentadienyl. R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ represent a hydrogen atom, a carbon atom having 1 to 30 carbon atoms, or a substituted cyclopentadienyl group. An organic silicon group having a hydrogen group or a hydrocarbon having 1 to 30 carbon atoms as a substituent, and may be the same or different. In addition, R ²⁹ , R ³⁰ , R ³¹ , or R ³² , R ³³ , R ³⁴ , or R ³⁵ , R ³⁶ , R ³⁷ are bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). It may be formed. However, at least one of R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ is a substituent other than a hydrogen atom. M ³ represents a transition metal of Group 4 of the periodic table. ] 5. The method according to claim 4, wherein R ²⁹ , R ³⁰ , R ³¹ , or R ³² , R ³³ , R ³⁴ , or R ³⁵ , R ³⁶ , R ³⁷ are bonded to carbons adjacent to the first, second, and third positions. Transition metal compounds. Three substituted cyclopentadienyl _group, the _{^{(C 5 H 2 R 29 R}} 30 R 31), (C 5 H 2 R 32 R 33 R 34), and _{^{(C 5 H 2 R 35 R}} 36 R 37), The transition metal compound according to claim 5, which has the same structure. The transition metal compound according to claim 1, having a structure represented by the following general formula (4).
_{^{(C 5 H 3 R 38 R}} 39) (C 5 H 3 R 40 R 41) (C 5 H 3 R 42 R 43) M 4 H
... Equation (4)
[Wherein (C ₅ H ₃ R ³⁸ R ³⁹ ), (C ₅ H ₃ R ⁴⁰ R ⁴¹ ), and (C ₅ H ₃ R ⁴² R ⁴³ ) each represent a cyclopentadienyl group or a substituted cycloalkyl group; Represents a pentadienyl group, and R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms as a substituent; Organosilicon groups which may be the same or different. Further, R ³⁸ and R ³⁹ , or R ⁴⁰ and R ⁴¹ , or R ⁴² and R ⁴³ may be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). However, at least one of R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ is a substituent other than a hydrogen atom. M ⁴ represents a transition metal of Group ⁴ of the periodic table. ] Three substituted cyclopentadienyl _{^{group, (C 5 H 3 R 38}} R 39), is _{^{(C 5 H 3 R 40 R}} 41), and _{^{(C 5 H 3 R 42 R}} 43), wherein the same structure Item 8. The transition metal compound according to Item 7. The transition metal compound according to claim 1, which has a structure represented by the following general formula (5).
_{^{(C 9 R 44 R 45 R}} 46 R 47 R 48 R 49 R 50) (C 9 R 51 R 52 R 53 R 54 R 55 R 56 R 57) (C 9 R 58 R 59 R 60 R 61 R 62 R ⁶³ R ⁶⁴ ) M ⁵ H
... Equation (5)
[Wherein (C ₉ R ⁴⁴ R ⁴⁵ R ⁴⁶ R ⁴⁷ R ⁴⁸ R ⁴⁹ R ⁵⁰ ), (C ₉ R ⁵¹ R ⁵² R ⁵³ R ⁵⁴ R ⁵⁵ R ⁵⁶ R ⁵⁷ ) and (C ₉ R ⁵⁸ R ⁵⁹⁾ R ⁶⁰ R ⁶¹ R ⁶² R ⁶³ R ⁶⁴ ) each represents an indenyl group or a substituted indenyl group, and R ^{44 to} R ⁶⁴ represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a carbon group having 1 to 30 carbon atoms. These are organosilicon groups having hydrogen as a substituent, and may be the same or different. Further, among these ^R 44 ^{to R 50} or ^R 51 ^{to R 57,} or ^R 58 ^{to R 64} may be combined with each other to form a cyclic hydrocarbon group (including polycyclic structure). M ⁵ represents a periodic table group IV transition metals. ] The transition metal compound according to claim 1, which has a structure represented by the following general formula (6).
_{^{(C 9 H 3 R 65 R}} 66 R 67 R 68) (C 9 H 3 R 69 R 70 R 71 R 72) (C 9 H 3 R 73 R 74 R 75 R 76) M 6 H
... Equation (6)
[Wherein (C ₉ H ₃ R ⁶⁵ R ⁶⁶ R ⁶⁷ R ⁶⁸ ), (C ₉ H ₃ R ⁶⁹ R ⁷⁰ R ⁷¹ R ⁷² ) and (C ₉ H ₃ R ⁷³ R ⁷⁴ R ⁷⁵ R ⁷⁶ ) are each Represents an indenyl group or a substituted indenyl group, and R ^{65 to} R ⁷⁶ are a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or an organosilicon group having a hydrocarbon group having 1 to 30 carbon atoms as a substituent; They may be the same or different. Among them, R ^{65 to} R ⁶⁸ , R ^{69 to} R ⁷² , and R ^{73 to} R ⁷⁶ are bonded to the 4-, 5-, 6-, and 7-positions (6-membered ring portions) of the respective indenyl groups. May be bonded to each other to form a cyclic hydrocarbon group (including a polycyclic structure). M ⁶ represents a transition metal of Group 4 of the periodic table. ] 3 substituted indenyl _{^{group, (C 9 H 3 R 65}} R 66 R 67 R 68), (C 9 H 3 R 69 R 70 R 71 R 72) and ^{_{(C 9 H 3 R 73 R}} 74 R 75 R 76) Have the same structure.   The transition metal compound according to any one of claims 1 to 11, wherein the transition metal of Group 4 of the periodic table is Zr.   An olefin polymerization catalyst comprising the transition metal compound according to any one of claims 1 to 12, and an organoaluminum oxy compound and / or a compound that reacts with the transition metal compound to form an ion pair.   The catalyst for olefin polymerization according to claim 13, wherein the organic aluminum oxy compound is methylaluminoxane.   An olefin polymerization catalyst, wherein the catalyst according to claim 13 or 14 is a solid catalyst supported on a carrier.   13. An olefin polymerization catalyst, which is a solid catalyst in which the transition metal compound according to claim 1 is supported on a layered silicate.   A method for producing a polyolefin, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 13 to 16. The method for producing a polyolefin according to claim 17, wherein the polymerization of the olefin according to claim 17 is homopolymerization of ethylene or copolymerization of ethylene with an α-olefin.

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