JP2015189713A - Fluorene compound, transition metal compound, catalyst for olefin polymerization and manufacturing method for olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel fluorene compound useful as an intermediate of a transition metal compound for olefin polymerization, for a catalyst for olefin polymerization capable of polymerizing at high temperature, a transition metal compound having the fluorene ring as a partial structure as a catalyst component for olefin polymerization, the catalyst for olefin polymerization containing the transition metal compound and a method for manufacturing the olefin polymer.SOLUTION: There is provided a fluorene transition metal complex compound represented by a structure of the following 2A-2 as an example of a transition metal compound which becomes the catalyst for olefin polymerization.

Description

  The present invention relates to a novel fluorene compound, a transition metal compound containing the fluorene compound as a partial structure, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer using the olefin polymerization catalyst.

[Metalocene compounds]
A process for producing an olefin polymer using a transition metal compound having a cyclopentadienyl ligand or a substituted cyclopentadienyl ligand as a catalyst for olefin polymerization, a so-called metallocene compound is widely known. Since it was reported by W. Kaminsky et al. That a catalyst based on a combination of zirconocene dimethyl and methylaluminoxane (MAO) shows high activity in the polymerization of ethylene [Non-Patent Document 1], the performance of the catalyst and the unique polymer Various improvements have been attempted for the purpose of manufacturing. Of these, many studies have been conducted on the method of stereoregularly polymerizing α-olefins since isotactic polymerization was reported by W. Kaminsky et al. (See Non-Patent Document 2).

  In the polymerization of α-olefin using a metallocene compound, it can be obtained by introducing a substituent into the cyclopentadienyl ring of the ligand of the metallocene compound or by crosslinking two cyclopentadienyl rings. It is known that the stereoregularity and molecular weight of α-olefin polymers vary greatly.

[Metalocene compounds having a fluorene ring]
For example, the following reports have been made on the case where a metallocene compound having a ligand in which a cyclopentadienyl ring and a fluorenyl ring are bridged is used as a catalyst for propylene polymerization.

  From the viewpoint of stereoregularity, in dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, syndiotactic polypropylene (see Non-Patent Document 3) introduced a methyl group at the 3-position of the cyclopentadienyl ring. In dimethylmethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, hemiisotactic polypropylene (see Patent Document 1) is a dimethylmethylene (3) in which a tert-butyl group is introduced at the 3-position of the cyclopentadienyl ring. With -tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isotactic polypropylene (see Patent Document 2) can be obtained.

  In addition, dimethylmethylene (3-tert-butyl) introduced a tert-butyl group at the 3,6-position of the fluorenyl ring rather than dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride. -5-Methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride provides a polypropylene (see Patent Document 3) with improved isotactic stereoregularity.

Also, from the viewpoint of molecular weight, diphenylmethylene (cyclopentadienyl) in which the bridge between the cyclopentadienyl ring and the fluorenyl ring is changed to diphenylmethylene rather than dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. ) (Fluorenyl) zirconium dichloride crosslinks higher molecular weight syndiotactic polypropylene (see Patent Document 4) than dimethylmethylene (3- (2-adamantyl) -cyclopentadienyl) (fluorenyl) zirconium dichloride. Diphenylmethylene (3- (2-adamantyl) -cyclopentadienyl) (fluorenyl) zirconium dichloride, whose part is changed to diphenylmethylene, has a higher molecular weight isotactic-hemiisotactic polypropylene (see Non-Patent Document 4) ) With dimethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride introduced with a methyl group at the 5-position of the cyclopentadienyl ring (the α-position of the bridge). With tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, it is possible to obtain high molecular weight isotactic polypropylene (see Patent Document 5).

  In addition, dimethylmethylene (3-tert-butyl-2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride and diphenylmethylene (3,4-methyl) introduced with substituents at two adjacent positions on the cyclopentadienyl ring. In dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride and diphenylmethylene (3-methylcyclopentadienyl) (fluorenyl) respectively. ) Compared with zirconium dichloride, polypropylene having a low molecular weight is obtained (see Patent Documents 5 to 6).

  As described above, there are many reported examples of metallocene compounds having a ligand in which a cyclopentadienyl ring and a fluorenyl ring are bridged. On the other hand, there are no reports of synthesis and polymerization of metallocene compounds in which the 2,3-position, 6,7-position of the fluorene ring forms a 1,2-dihydropyridine ring structure. In addition, fluorene derivatives having a 1,2-dihydropyridine ring only at the 2,3-position are known (Non-Patent Document 5), but the 1,2-dihydropyridine ring is at the 2,3-position, 6,7-position. There is no report on the synthesis of the fluorene derivative having the above. Therefore, it has not been known what kind of performance such a metallocene compound has.

On the other hand, when focusing on the central metal, it is widely known that a hafnium compound produces a high-molecular-weight olefin polymer as compared with a zirconium compound having the same structure. Japanese Examined Patent Publication No. 6-811 discloses that the molecular weight of polyethylene produced as compared with zirconocene dichloride is improved by using hafnocene dichloride as the metallocene compound. Also Patent No. 2882257 discloses, [isopropylidene - (- fluorenyl eta ⁵⁾ (eta ⁵ cyclopentadienyl)] by using a hafnium dichloride, [isopropylidene (eta ⁵ - cyclopentadienyl) (eta ⁵ It is disclosed that the molecular weight of the ethylene / 1-hexene copolymer produced compared to -fluorenyl)] zirconium dichloride is improved. However, in any of these cases, the molecular weight of the olefin polymer produced is not sufficient, and it has been difficult to produce an olefin polymer having a desired molecular weight at a high temperature that is industrially useful. W. Kaminsky et al. Further improved the molecular weight of the resulting polypropylene by introducing substituents into the bridging and fluorenyl groups of the bridged cyclopentadienyl-fluorenyl metallocene compound [J. Organomet Chem., 684, 200 (2003)]. Although this attempt has achieved a certain result, the tendency of the molecular weight of the produced polypropylene to decrease with an increase in the polymerization temperature is remarkable, and a desired high molecular weight polypropylene has not been obtained by the intended high temperature polymerization.

  In general, when polymerized at a high temperature, the molecular weight of the resulting polymer tends to decrease, while the viscosity of the polymerization solution containing the generated olefin polymer decreases, and operations such as stirring become easy, and There is an advantage that the heat removal cost of reaction heat is reduced, and the economy is improved. Furthermore, when removing the solvent and monomer remaining after polymerization, it can be efficiently removed with less heating. Therefore, development of a more highly active polymerization catalyst and polymerization method capable of obtaining a higher molecular weight polymer is desired.

  From the viewpoint of removing the residual monomer, it is also effective to reduce the residual amount of the high-boiling monomer after the polymerization in addition to performing the polymerization at a high temperature. In particular, since monomers such as cyclic olefins and polyenes having a cyclic skeleton have a relatively high boiling point, the development of a catalyst and a polymerization method capable of efficiently polymerizing them is also important.

  On the other hand, fluorene compounds having a nitrogen-containing group at the 2,7-position have recently been used in organic electroluminescent devices and the like (see Patent Document 7).

Japanese Patent Laid-Open No. 03-193796 Japanese Unexamined Patent Publication No. 06-122718 International Publication No. 2001/027124 Japanese Patent Laid-Open No. 02-274703 Special table 2001-526730 Japanese Patent Laid-Open No. 10-226694 JP 05-25473 A

Angew. Chem. Int. Ed. Engl., 19, 390 (1980) Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 110, 6255 (1988) Organometallics, 21, 934 (2002) Bioorg. Med. Chem. Lett., 8, 2731-2736 (1998)

  The present invention provides a novel fluorene compound useful as an intermediate of a transition metal compound used as an olefin polymerization catalyst, a transition metal compound having the fluorene ring as a partial structure as a catalyst component for olefin polymerization, and the transition metal compound. An object of the present invention is to provide a catalyst for olefin polymerization and a method for producing an olefin polymer. Furthermore, the present invention can efficiently produce a high-molecular-weight olefin polymer, and when a polyene is used in combination with the raw material monomer, an olefin polymer having a high polyene content can be efficiently obtained at a high polyene monomer conversion rate. PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization and a method for producing the olefin polymer, a transition metal compound used for the catalyst for olefin polymerization, and a novel fluorene compound useful as an intermediate of the transition metal compound, which can be produced well. It is an object.

  The present inventor has intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using an olefin polymerization catalyst containing a transition metal compound having the following constitution, and the present invention has been completed. The gist of the present invention is as follows.

[1]
A fluorene compound represented by the following general formula [I]:

（式中、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵およびR¹⁶は、水素原子、炭化水素基、ケイ素含有基およびヘテロ原子含有炭化水素基から選ばれ、それぞれ同一であっても異なっていてもよい。
R¹からR¹⁶までの隣接した置換基は、互いに結合して環を形成してもよい。）

(Where 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 , R ¹⁵ and R ¹⁶ is selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing hydrocarbon group, and may be the same or different.
Adjacent substituents from R ¹ to R ¹⁶ may be bonded to each other to form a ring. )

[2]
A fluorene compound represented by the following general formula [I ′]:

（式中、R⁰は金属含有基であり、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵およびR¹⁶は、水素原子、炭化水素基、ケイ素含有基およびヘテロ原子含有炭化水素基から選ばれ、それぞれ同一であっても異なっていてもよい。
R⁰とR²とは、互いに結合して環を形成してもよく、R²からR¹⁶までの隣接した置換基は、互いに結合して環を形成してもよい。）

(Wherein R ⁰ is a metal-containing group, 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 , R ¹⁵ and R ¹⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing hydrocarbon group, and may be the same or different.
R ⁰ and R ² may be bonded to each other to form a ring, and adjacent substituents from R ² to R ¹⁶ may be bonded to each other to form a ring. )

[3]
A transition metal compound represented by the following general formula [II]:

（式中、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹およびR²²は、水素原子、炭化水素基、ケイ素含有基およびヘテロ原子含有炭化水素基から選ばれ、それぞれ同一であっても異なっていてもよく、R¹⁷からR²²までの隣接した置換基は、互いに結合して環を形成してもよい。

Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing hydrocarbon group, The adjacent substituents from R ¹⁷ to R ²² may be different from each other to form a ring.

  M is a Group 4 transition metal atom, Y is a carbon atom, a silicon atom or a germanium atom, Q is a neutral coordination that can be coordinated by a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron pair The same or different combinations are selected from the children, and j is an integer of 1 to 4.

Z is a fluorenylidene group having a divalent free valence having a structure obtained by removing R ¹ and R ² in the general formula [I] from the fluorene compound described in [1] above. )

[4]
The transition metal compound according to the above [3], wherein in the general formula [II], R ¹⁹ , R ²⁰ , R ²¹ and R ²² are hydrogen atoms.

[5]
In the general formula [I], R ³ , R ⁹ , R ¹⁰ and R ¹⁶ are hydrogen atoms, wherein the transition metal compound according to the above [3] or [4].

[6]
The catalyst for olefin polymerization containing the transition metal compound as described in any one of [3] to [5] above.

[7]
(B-1) organometallic compounds,
It further contains (B-2) an organoaluminum oxy compound, and (B-3) at least one compound (B) selected from compounds that react with the transition metal compound described in [3] to form an ion pair. The olefin polymerization catalyst according to the above [6].

[8]
Including the step of polymerizing one or more olefins selected from ethylene and an α-olefin having 3 to 30 carbon atoms in the presence of the olefin polymerization catalyst according to [6] or [7], A method for producing an olefin polymer, wherein at least one kind is ethylene or propylene.

[9]
The method for producing an olefin polymer according to the above [8], wherein the step of polymerizing the olefin in the presence of polyene is carried out.

  By using the catalyst for olefin polymerization according to the present invention, a high-molecular-weight olefin polymer can be produced efficiently. Also, when polyene is used in combination with the raw material monomer, the polyene monomer can be converted at a high polyene monomer conversion rate. A high olefin polymer can be produced efficiently.

  In addition, by using the fluorene compound and the transition metal compound according to the present invention, a useful catalyst for olefin polymerization can be provided as described above.

Hereinafter, the present invention will be described in more detail.
[Fluorene compounds [I] and [I ']]
The fluorene compound [I] according to the present invention is represented by the following general formula [I].

（式中、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵およびR¹⁶は、水素原子、炭化水素基、ケイ素含有基およびヘテロ原子含有炭化水素基から選ばれ、それぞれ同一であっても異なっていてもよい。
R¹からR¹⁶までの隣接した置換基は、互いに結合して環を形成してもよい。）

(Where 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 , R ¹⁵ and R ¹⁶ is selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing hydrocarbon group, and may be the same or different.
Adjacent substituents from R ¹ to R ¹⁶ may be bonded to each other to form a ring. )

Examples of the hydrocarbon group in R ¹ to R ¹⁶ include one or more linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and saturated hydrocarbon groups. And a group formed by substituting a hydrogen atom of a cyclic unsaturated hydrocarbon group. The carbon number of the hydrocarbon group is usually 20 or less, preferably 15 or less, more preferably 10 or less, and the lower limit is 1 for a linear hydrocarbon group and 3 for a branched hydrocarbon group. 3 is a cyclic saturated hydrocarbon group, 3 is a cyclic unsaturated hydrocarbon group, or a group obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. 4 is.

  Examples of the linear hydrocarbon group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. A linear alkyl group such as an n-decanyl group; a linear alkenyl group such as an allyl group.

  Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

  Examples of the cyclic unsaturated hydrocarbon group include aryl groups such as a phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group; cycloalkenyl groups such as a cyclohexenyl group; 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

  Examples of the group formed by substituting one or more hydrogen atoms of the saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include, for example, a benzyl group, a cumyl group, a 1,1-diphenylethyl group, a triphenylmethyl group, and the like. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

Examples of the hetero atom-containing hydrocarbon group in R ¹ to R ¹⁶ include an oxygen atom-containing hydrocarbon group such as an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, a furyl group, and a methoxyphenyl group; N-methylamino group, N, N-dimethylamino group, amino group such as N-phenylamino group, nitrogen atom-containing hydrocarbon group such as pyryl group, dimethylaminophenyl group; sulfur atom such as thienyl group, methylthiophenyl group And halogen-containing hydrocarbon groups such as a containing hydrocarbon group, a trifluoromethyl group, a pentafluoromethyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group. Carbon number of a hetero atom containing hydrocarbon group is 1-20 normally, Preferably it is 2-18, More preferably, it is 2-15. However, the silicon-containing group is excluded from the heteroatom-containing hydrocarbon group.

Examples of the silicon-containing group in R ¹ to R ¹⁶ include a formula —SiR ₃ such as a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group (wherein a plurality of R are each Independently an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 15 carbon atoms.).
The fluorene compound [I ′] according to the present invention is represented by the following general formula [I ′].

（式中、R⁰は金属含有基であり、R²〜R¹⁶は、それぞれ前記一般式[I]における同一記号と同義である。
R⁰とR²とは、互いに結合して環を形成してもよく、R²からR¹⁶までの隣接した置換基は、互いに結合して環を形成してもよい。）

(In the formula, R ⁰ is a metal-containing group, and R ^{2 to} R ¹⁶ have the same meanings as those in the general formula [I].
R ⁰ and R ² may be bonded to each other to form a ring, and adjacent substituents from R ² to R ¹⁶ may be bonded to each other to form a ring. )

As the metal-containing group, together with the fluorenylidene group derived by removing R ⁰ and R ² in the general formula [I ′] from the fluorene compound [I ′], a metallocene compound having the fluorenylidene group as one of the ligands is formed. Substituents are preferred. Examples of the metal contained in the metal-containing group include chromium, iron, cobalt, nickel, vanadium, molybdenum, tungsten, zinc, scandium, yttrium, lanthanum, lanthanoids, group 4 transition metals such as titanium, zirconium, hafnium, lithium, and the like. , Groups having alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium and calcium. In addition to these metals, metal-containing groups include cyclopentadienyl groups, indenyl groups, azulenyl groups, and groups in which the above-described hydrocarbon groups, heteroatom-containing hydrocarbon groups, silicon-containing groups, etc. are substituted. May be. In addition, as ligands that coordinate to metals, carbon monoxide, organic phosphorus ligands such as triphenylphosphine, halogen ligands such as chlorine, organic amine ligands such as dimethylamide groups, etc. Also good.

  Specific examples of the fluorene compound [I ′] include the compound (5) represented by the following formula. Here, L is a metal-containing group such as lithium, sodium, potassium, magnesium chloride (MgCl), magnesium bromide (MgBr), zinc chloride (ZnCl), zirconium trichloride, hafnium trichloride, titanium trichloride, cyclopenta. Examples include dienyldichlorozirconium, cyclopentadienyldichlorohafnium, cyclopentadienyldichlorotitanium, cyclopentadienyliron, etc., preferably lithium, sodium, potassium, magnesium, zinc, titanium, zirconium, hafnium-containing substituents It is a group.

（R³からR¹⁶までの置換基のうち、隣接した２つの置換基（例：R³とR⁴、R⁴とR⁵、R⁵とR⁶、R⁶とR⁷、R⁷とR⁸、R⁸とR⁹、R⁹とR¹⁰、R¹⁰とR¹¹、R¹¹とR¹²、R¹²とR¹³、R¹³とR¹⁴、R¹⁴とR¹⁵、R¹⁵とR¹⁶）が互いに結合して環を形成していてもよい。前記環は、分子中に２箇所以上形成されていてもよい。）

(Of the substituents from R ³ to R ¹⁶ , two adjacent substituents (eg, R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ) May be bonded to each other to form a ring, which may be formed in two or more places in the molecule.)

  In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a hetero ring such as a furan ring and a thiophene ring, and a corresponding hydrogenated hetero ring, such as a cyclohexane ring, a benzene ring, and a hydrogenated benzene. A ring is preferred.

  The fluorene compound [I ′] may have a cyclic structure containing a metal. Examples of the fluorene compound [I ′] having a cyclic structure containing a metal include the following compound (10a).

（Aは窒素原子またはリン原子であり、R¹⁷、R¹⁸およびR²³は、それぞれ独立に、水素原子ならびに上述した炭化水素基、ケイ素含有基、ヘテロ原子含有炭化水素基から選ばれる置換基であり、Y、M、Qおよびjは、それぞれ後述する一般式[II]における同一記号と同義である。）

(A is a nitrogen atom or a phosphorus atom, and R ¹⁷ , R ¹⁸ and R ²³ are each independently a hydrogen atom and a substituent selected from the above-described hydrocarbon group, silicon-containing group, and heteroatom-containing hydrocarbon group. Y, M, Q, and j are synonymous with the same symbols in general formula [II] described later.)

  Examples of the compound (10a) include a compound represented by the following formula.

式[I]および[I']において、R³、R⁷、R⁹、R¹⁰、R¹²およびR¹⁶は水素原子であることが好ましい。R⁴、R⁵、R⁶、R⁸、R¹¹、R¹³、R¹⁴およびR¹⁵としては炭化水素基およびヘテロ原子含有炭化水素基が好ましく、炭化水素基がより好ましく、隣接する炭化水素基同士が互いに結合せず環を形成していないことがさらに好ましい。

In the formulas [I] and [I ′], R ³ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁶ are preferably hydrogen atoms. R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁵ are preferably hydrocarbon groups and heteroatom-containing hydrocarbon groups, more preferably hydrocarbon groups, and adjacent hydrocarbon groups. More preferably, they are not bonded to each other and do not form a ring.

<Examples of Preferred Fluorene Compounds [I] and [I ']>
Preferred fluorene compounds [I] and [I ′] according to the present invention include, for example,
2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,4-g ′] diquinoline, 12,12-diethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinoline, 12 , 12-Dioctyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-2,9,10,12-tetrahydro- 1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,10-dimethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-1,10-dimethyl 2,9,10 , 12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-1,10-dimethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,10-dimethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-diphenyl-1,10-dimethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g'] diquinoline,
2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-2, 2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-2,2, 4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,2,4,7,9,10-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-1, 2,4,7,9,10-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-1,2, 4,7,9,10-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,2,4, 7,9,10-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1,2,4,7, 9,10-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
2,2,9,9-Tetramethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-2,2,9 , 9-Tetramethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-2,2,9,9-tetramethyl 2,9,10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-2,2,9,9-tetramethyl 2,9,10 , 12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-2,2,9,9-tetramethyl 2,9,10,12-tetrahydro- 1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
2,2,9,9-Tetramethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dimethyl-2,2,9 , 9-Tetramethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-2,2,9,9-tetramethyl 2,9,10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-2,2,9,9-tetramethyl 2,9,10 , 12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-2,2,9,9-tetramethyl 2,9,10,12-tetrahydro- 1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12- Dimethyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12, 12-diethyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinoline, 12,12-dioctyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-diphenyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g '] Diquinoline,
1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12, 12-dimethyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-diethyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4 -g '] diquinoline, 12,12-dioctyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diphenyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,5-g '] diquinoline,
1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-dimethyl-1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diethyl-1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H -Cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1,10-di-iso-propyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-dimethyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diethyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H -Cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1,10-di-n-propyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-dimethyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diethyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H -Cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1,10-di-n-propyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12, 12-dimethyl-1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-diethyl-1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4 -g '] diquinoline, 12,12-dioctyl-1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diphenyl-1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,5-g '] diquinoline,
1,12-di-n-octyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4 -g '] diquinoline, 12,12-dimethyl-1,12-di-n-octyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H -Cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-1,12-di-n-octyl-1,2,2,4,7,9,9,10- Octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,12-di-n-octyl-1,2, 2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1, 12-di-n-octyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g '] Diquinoline,
1,12-diphenyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinoline, 12,12-dimethyl-1,12-diphenyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinoline, 12,12-diethyl-1,12-diphenyl-1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H -Cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,12-diphenyl-1,2,2,4,7,9,9,10-octamethyl 2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diphenyl-1,12-diphenyl-1,2,2,4,7,9, 9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,5-g ′] diquinoline,
1,12-di-n-octyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5 , 4-g '] diquinoline, 12,12-dimethyl-1,12-di-n-octyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12 -Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-diethyl-1,12-di-n-octyl-1,10-diethyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline, 12,12-dioctyl-1,12-di-n- Octyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinoline, 12,12-diphenyl-1,12-di-n-octyl-1,10-diethyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,5-g '] diquinoline,
[(Tert-butylamino) (1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] Diquinolin-12-yl) dimethylsilane)] titanium dichloride, [(tert-butylamino) (1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro- 1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) dimethylsilane)] zirconium dichloride, [(tert-butylamino) (1,2,2,4,7,9, 9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl) dimethylsilane)] hafnium dichloride.

However, the fluorene compounds [I] and [I ′] are not limited to the compounds exemplified above.
The fluorene compounds [I] and [I ′] according to the present invention are used as intermediates for the transition metal compound [II] described later. The fluorene compounds [I] and [I ′] according to the present invention are also useful in the field of organic electroluminescence devices.

[Transition metal compound [II]]
The transition metal compound [II] according to the present invention is represented by the following general formula [II].

（式中、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²¹およびR²²は、水素原子、炭化水素基、ケイ素含有基およびヘテロ原子含有炭化水素基から選ばれ、それぞれ同一であっても異なっていてもよく、R¹⁷からR²²までの隣接した置換基は、互いに結合して環を形成してもよい。
Mは第4族遷移金属原子であり、Yは炭素原子、ケイ素原子またはゲルマニウム原子であり、Qはハロゲン原子、炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、jは1〜4の整数である。
Zは、本発明に係るフルオレン化合物[I]から一般式[I]におけるR¹およびR²を除いた構造を有する、２価の遊離原子価を持つフルオレニリデン基である。）

Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing hydrocarbon group, The adjacent substituents from R ¹⁷ to R ²² may be different from each other to form a ring.
M is a Group 4 transition metal atom, Y is a carbon atom, a silicon atom or a germanium atom, Q is a neutral coordination that can be coordinated by a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron pair The same or different combinations are selected from the children, and j is an integer of 1 to 4.
Z is a fluorenylidene group having a divalent free valence having a structure obtained by removing R ¹ and R ² in the general formula [I] from the fluorene compound [I] according to the present invention. )

  That is, the transition metal compound [II] according to the present invention is represented by the following general formula [IIa].

<R ³ to R ²² >
Details (specific examples, preferred embodiments, etc.) of the hydrocarbon group, silicon-containing group and heteroatom-containing hydrocarbon group as R ³ to R ²² are respectively the hydrocarbon group as R ¹ to R ¹⁶ and the silicon-containing group described above. The details of the group and the heteroatom-containing hydrocarbon group are the same. Of the substituents R ³ to R ²² , two adjacent substituents may be bonded to each other to form a ring. Two or more rings may be formed in the molecule.

R ³ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁶ are preferably hydrogen atoms, and R ¹⁹ , R ²⁰ , R ²¹ and R ²² are more preferably hydrogen atoms.
R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁵ are preferably hydrocarbon groups, and the hydrocarbon groups are more preferably linear alkyl groups, More preferably, the hydrocarbon groups to be bonded do not bond to each other to form a ring, and R ¹⁷ and R ¹⁸ are preferably a cyclic unsaturated hydrocarbon group or a heteroatom-containing hydrocarbon group.

<Y>
Y is selected from a carbon atom, a silicon atom and a germanium atom, preferably a carbon atom or a silicon atom, and particularly preferably a carbon atom.

<M, Q, j>
M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Hf.

Q is selected in the same or different combination from a halogen atom, a hydrocarbon group, an anionic ligand and a neutral ligand capable of coordinating with a lone pair of electrons.
Examples of the halogen atom for Q include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group for Q include the same groups as the hydrocarbon groups for R ¹ to R ^22, and an alkyl group such as a linear alkyl group or a branched alkyl group is preferable.
Examples of the anionic ligand in Q include alkoxy groups such as methoxy group and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate group and benzoate group; sulfonate groups such as mesylate group and tosylate group; Amide groups such as dimethylamide group, diisopropylamide group, methylanilide group, diphenylamide group and the like can be mentioned.

Examples of the neutral ligand capable of coordinating with a lone electron pair in Q include, for example, organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2- Examples include ethers such as dimethoxyethane.
At least one Q is preferably a halogen atom or an alkyl group.
j is an integer of 1 to 4, preferably 2.

The preferred embodiments of the configuration of the transition metal compound [II], that is, R ^{3 to} R ²² , Y, M, Q, and j have been described above. In the present invention, any combination of each preferred embodiment is also a preferred embodiment, wherein R ³ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁶ are hydrogen atoms, Y is a carbon atom, and M is The combination that is Zr or Hf is more preferable, and R ³ , R ⁷ , R ⁹ , R ¹⁰ , R ¹² , R ¹⁶ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are hydrogen atoms, and Y is a carbon atom. And the combination in which M is Zr or Hf is more preferred.

  In the olefin polymerization using the olefin polymerization catalyst containing the transition metal compound [II] described above, a polymer having a high molecular weight is obtained particularly when used as a component in the copolymerization of ethylene and an α-olefin having 3 or more carbon atoms. In addition, in the copolymerization of ethylene or α-olefin and a cyclic olefin (including a polyene having a cyclic skeleton), the cyclic olefin is easily incorporated.

Many studies have been conducted on the influence of the catalyst structure on the catalyst performance (for example, Coord. Chem. Rev., 25, 18-35, (2006)). In particular, verification of the structure and performance of the catalyst by first-principles calculations has been actively performed recently. For example, Organometallics, 30, 1350-1358, (2011) show that the molecular weight of the polymer obtained and the ease of incorporation of the comonomer correlate with the activation energy of the transition state in the elementary reaction of the polymerization. That is, the molecular weight of the obtained polymer correlates with the difference in activation energy between the main chain growth reaction (monomer insertion reaction) and the termination reaction (β-hydrogen transfer reaction). It can be said that the larger this difference is, the easier the main chain growth reaction occurs than the termination reaction, that is, the higher the molecular weight of the polymer. In the transition metal compound of the present invention and a known transition metal compound, activation is assumed when a catalytically active species represented by the following formula (isobutyl group is adopted as a model of the polymer main chain) and ethylene is inserted into them. The difference between the energy (G _Eins ) and the activation energy (G _EH ) when a β-hydrogen transfer reaction occurs in ethylene (G _EH -G _Eins ), the activation when a β-hydrogen transfer reaction occurs in a hafnium atom The results of calculating the energy (G _MH ) by the density functional method are shown in the table below.

Similarly, the ease of comonomer incorporation is correlated with the difference in the activation energy of the ethylene and comonomer insertion reaction. That is, if this difference is small, the comonomer can be more easily incorporated. The density functional of the difference (G _Nins -G _Eins ) between the activation energy (G _Eins ) when inserting ethylene into the catalytically active species as shown in the figure and the activation energy (G _Nins ) when inserting norbornene The results calculated by the method are shown in the table below.

  From these theoretical calculations, cyclic olefins are used in the copolymerization of ethylene and α-olefins having 3 or more carbon atoms, or in the copolymerization of ethylene or α-olefins with cyclic olefins. It is supported that the fluorene compound and the transition metal compound of the present invention are useful in easily taking in

<Examples of Preferred Transition Metal Compound [II]>
Preferred transition metal compounds [II] according to the present invention include, for example,
[(Cyclopentadienyl) (diphenylmethylene) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5 , 4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (diphenylmethylene) (1,10-diethyl-2,2,4,7,9,9-hexamethyl-2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (diphenylmethylene) (1,10- Di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline-12- Yl)] hafnium dichloride, [(cyclopentadienyl) (diphenylmethylene) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro -1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (diphenyl Methylene) (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline -12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (di (p-methylphenyl)) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-methylphenyl)) (1,10-diethyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl ) (Di (p-methylphenyl)) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-methylphenyl)) (1,10-di-n-propyl-2, 2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [( Cyclopentadie ) (Di (p-methylphenyl)) (1,10-phenyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinolin-12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (di (p-methoxyphenyl)) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-methoxyphenyl)) (1,10-diethyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl ) (Di (p-methoxyphenyl)) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-methoxyphenyl)) (1,10-di-n-propyl-2, 2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [( Cyclope Tadienyl) (di (p-methoxyphenyl)) (1,10-phenyl-2,2,4,7,9,9-hexamethyl2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinolin-12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (di (p-fluorophenyl)) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-fluorophenyl)) (1,10-diethyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl ) (Di (p-fluorophenyl)) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (di (p-fluorophenyl)) (1,10-di-n-propyl-2, 2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [( Cyclope Tadienyl) (di (p-fluorophenyl)) (1,10-phenyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinolin-12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (bis (p-dimethylaminophenyl)) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1 , 2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (bis (p-dimethylaminophenyl)) (1,10-diethyl-2,2, 4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopenta Dienyl) (bis (p-dimethylaminophenyl)) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (bis (p-dimethylaminophenyl)) (1,10-di-n- Propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] ha Funium dichloride, [(cyclopentadienyl) (bis (p-dimethylaminophenyl)) (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro -1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (isopropylidene) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5 , 4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (isopropylidene) (1,10-diethyl-2,2,4,7,9,9-hexamethyl-2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (isopropylidene) (1,10- Di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline-12- Yl)] hafnium dichloride, [(cyclopentadienyl) (isopropylidene) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro -1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (isopropylidene) (1,10-Phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline-12 -Ill)] hafnium dichloride,
[(Cyclopentadienyl) (1,2-ethylidene) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2- g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (1,2-ethylidene) (1,10-diethyl-2,2,4,7,9, 9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (1, 2-ethylidene) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5, 4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (1,2-ethylidene) (1,10-di-n-propyl-2,2,4,7,9, 9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (1, 2-ethylidene) (1,10-phenyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride,
[(Cyclopentadienyl) (dimethylsilyl) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5 , 4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (dimethylsilyl) (1,10-diethyl-2,2,4,7,9,9-hexamethyl-2,9 , 10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (dimethylsilyl) (1,10- Di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline-12- Yl)] hafnium dichloride, [(cyclopentadienyl) (dimethylsilyl) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro -1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(cyclopentadienyl) (dimethylsilyl) (1,10-pheny 2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium Dichloride,
[(4-t-Butyl-2-methylcyclopentadienyl) (isopropylidene) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H- Cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (isopropylidene) (1,10- Diethyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium Dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (isopropylidene) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl 2,9, 10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) ( Isopropylidene) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4 -g '] Diquinoline-12-I )] Hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (isopropylidene) (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9, 10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride,
[(4-t-Butyl-2-methylcyclopentadienyl) (diphenylmethylene) (1,2,2,4,7,9,9,10-octamethyl-2,9,10,12-tetrahydro-1H- Cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (diphenylmethylene) (1,10- Diethyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium Dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (diphenylmethylene) (1,10-di-iso-propyl-2,2,4,7,9,9-hexamethyl-2,9, 10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) ( Diphenylmethylene) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4 -g '] N-12-yl)] hafnium dichloride, [(4-t-butyl-2-methylcyclopentadienyl) (diphenylmethylene) (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride,
[1- (1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline- 12-yl) (5- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydropentalene))] hafnium dichloride, [1- (1,10-diethyl-2, 2,4,7,9,9-Hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) (5- (tert- Butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydropentalene))] hafnium dichloride, [1- (1,10-di-iso-propyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) (5- (tert-butyl) -1,1 , 3-Trimethyl-1,2,3,3a-tetrahydropentalene))] hafnium dichloride, [1- (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl-2 , 9,10,12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) (5- (tert-butyl) -1,1,3-trimethyl-1 , 2,3, 3a-tetrahydropentalene))] hafnium dichloride, [1- (1,10-phenyl-2,2,4,7,9,9-hexamethyl-2,9,10,12-tetrahydro-1H-cyclopenta [1, 2-g: 5,4-g '] diquinolin-12-yl) (5- (tert-butyl) -1,1,3-trimethyl-1,2,3,3a-tetrahydropentalene))] hafnium dichloride ,
[1- (1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline- 12-yl) 5- (tert-butyl) -1-isopropyl-3-methyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [1- (1,10-diethyl-2,2, 4,7,9,9-Hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) 5- (tert-butyl)- 1-isopropyl-3-methyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [1- (1,10-di-iso-propyl-2,2,4,7,9,9- Hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) 5- (tert-butyl) -1-isopropyl-3-methyl- 1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [1- (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12 -Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) 5- (tert-butyl) -1-isopro Ru-3-methyl-1,2,3,3a-tetrahydropentalene)] hafnium dichloride, [1- (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10 , 12-Tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl) 5- (tert-butyl) -1-isopropyl-3-methyl-1,2,3, 3a-tetrahydropentalene)] hafnium dichloride, [8- (1,2,2,4,7,9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g : 5,4-g '] diquinolin-12-yl) 2- (tert-butyl) -8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene )] Hafnium dichloride,
[2- (tert-butyl) -8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene (1,10-diethyl-2,2,4, 7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [2- (tert- (Butyl) -8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene (1,10-di-iso-propyl-2,2,4,7, 9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [2- (tert-butyl) -8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene (1,10-di-n-propyl-2,2,4,7,9, 9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [2- (tert-butyl) -8 -Methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene (1,10-phenyl-2,2,4,7,9,9-hexamethyl-2 , 9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g ′] diquinolin-12-yl)] hafnium dichloride,
[1- (8-Methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene) adamantan-8-yl) (1,2,2,4,7, 9,9,10-octamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [1- (8- Methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene) adamantan-8-yl) (1,10-diethyl-2,2,4,7,9, 9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [1- (8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene) adamantan-8-yl) (1,10-di-iso-propyl-2,2,4,7,9, 9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinolin-12-yl)] hafnium dichloride, [1- (8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene) adamantane-8- ) (1,10-di-n-propyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4- g '] diquinolin-12-yl)] hafnium dichloride, [1- (8-methyl-3b, 4,5,6,7,7a, 8,8a-octahydrocyclopenta [a] indene) adamantane-8- Yl) (1,10-phenyl-2,2,4,7,9,9-hexamethyl 2,9,10,12-tetrahydro-1H-cyclopenta [1,2-g: 5,4-g '] diquinoline -12-yl)] hafnium dichloride.

  Examples of the transition metal compound [II] include titanium derivatives (hafnium substituted with titanium) and zirconium derivatives (hafnium substituted with zirconium) of the above-exemplified compounds. However, the transition metal compound [II] is not limited to the compounds exemplified above.

[Method for producing fluorene compounds [I] and [I ']]
The fluorene compounds [I] and [I ′] according to the present invention can be produced by using a known method, and the production method is not particularly limited. Below, an example of the manufacturing method of the fluorene compound [I] based on this invention is demonstrated first.

フルオレン化合物[I]は、例えば、上記反応[A]に示すように2,7-ジアミノフルオレン誘導体と、カルボニル化合物との反応により、合成することができる。カルボニル化合物としては公知のカルボニル化合物、または公知のα，β-不飽和カルボニル化合物を用いることができる（例えば、J. Org. Chem. 2006, 71, 1668-1676）。反応[A]において、2,7-ジアミノフルオレン誘導体とカルボニル化合物との反応は、2回以上に分けても良い。反応[A]では必要に応じて触媒を共存させてもよい。触媒としては、公知の酸、塩基、またはハロゲン化合物等が挙げられる。また反応を促進するために、反応系にマイクロ波を照射してもよい。フルオレン化合物[I]は、他の化合物との混合物として得られた場合には、従来公知の方法を利用して分離すればよい。

The fluorene compound [I] can be synthesized, for example, by reacting a 2,7-diaminofluorene derivative with a carbonyl compound as shown in the above reaction [A]. As the carbonyl compound, a known carbonyl compound or a known α, β-unsaturated carbonyl compound can be used (for example, J. Org. Chem. 2006, 71, 1668-1676). In the reaction [A], the reaction between the 2,7-diaminofluorene derivative and the carbonyl compound may be divided into two or more times. In the reaction [A], a catalyst may coexist if necessary. Examples of the catalyst include known acids, bases, halogen compounds and the like. In order to accelerate the reaction, the reaction system may be irradiated with microwaves. When the fluorene compound [I] is obtained as a mixture with other compounds, it may be separated using a conventionally known method.

  Known acids include hydrochloric acid, hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, trifluoromethanesulfonic acid, methanesulfonic acid, hydrofluoric acid, paratoluenesulfonic acid, perchloric acid, metaperiodic acid Examples thereof include acids and orthoperiodic acid. In addition, metal fluoride represented by boron fluoride, aluminum chloride, stannic chloride, ferric chloride, zinc chloride, cupric chloride, mercury chloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, odor Chlorides such as aluminum bromide, ferric bromide, beryllium chloride, gallium chloride, indium chloride, yttrium chloride, scandium chloride, and the metal trifluoromethanesulfonate, heteropolyacid, alumina, zeolite contained in these chlorides And solid acids such as

  Known bases include, for example, alkali metals such as sodium, potassium, and lithium; potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, barium hydroxide, sodium alkoxide, potassium alkoxide, magnesium hydroxide, magnesium alkoxide, Alkali metal or alkaline earth metal salts such as potassium hydride and sodium hydride; Nitrogenous bases such as diethylamine, ammonia, pyrrolidine, piperidine, aniline, methylaniline, triethylamine, lithium diisopropylamide, sodium amide; butyllithium, methyllithium Organic alkali metal compounds such as phenyl lithium; Grignard reagents such as methyl magnesium chloride, methyl magnesium bromide, and phenyl magnesium chloride. It is below.

Moreover, iodine, bromine, chlorine, fluorine, etc. are mentioned as a well-known halogen compound. One or more of these may be used simultaneously.
In reaction [A], a solvent may be used as necessary. The solvent to be used is not particularly limited, but aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and decalin; aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane , Ethers such as tert-butyl methyl ether and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; carboxylic acids such as formic acid, acetic acid and trifluoroacetic acid; esters such as ethyl acetate and methyl acetate; triethylamine, pyrrolidine and piperidine Amines such as aniline, pyridine, acetonitrile, nitriles or nitrogen-containing compounds; methanol, ethanol, n-propanol, isopropanol, n-butanol, isopropanol, ethylene glycol, methoxyethanol N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, N-methylpyrrolidone and other amides; Dimethyl sulfoxide; Sulfur-containing compounds such as carbon disulfide; Acetone, methyl ethyl ketone, etc. Ketones, especially aldehydes used as substrates, ketones themselves; non-organic solvents such as water and ionic liquids; or solvents obtained by mixing two or more of these, among these A solvent that does not inhibit the reaction can be selected.

When R ⁴ or R ¹⁵ bonded to the N atom of the fluorene compound obtained in the reaction [A] is a hydrogen atom, these hydrogen atoms may be converted into a substituent as necessary. For introducing the substituent, a known reaction can be used. For example, a reaction represented by the following reaction [B] can be used.

ここでXはフッ素、塩素、臭素、ヨウ素またはトリフレート基等の脱離基であり、R⁴およびR¹⁵は、それぞれ独立に前記炭化水素基、前記ケイ素含有基および前記ヘテロ原子含有炭化水素基から選ばれる基である。

Wherein X is a leaving group such as fluorine, chlorine, bromine, iodine or a triflate group, and R ⁴ and R ¹⁵ are each independently the hydrocarbon group, the silicon-containing group and the heteroatom-containing hydrocarbon group. Is a group selected from

  In reaction [B], a base may be used to accelerate the reaction. Known bases can be used, for example, alkali metals such as sodium, potassium and lithium; potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, barium hydroxide, sodium alkoxide, potassium alkoxide, water Alkali metal or alkaline earth metal salts such as magnesium oxide, magnesium alkoxide, potassium hydride, sodium hydride, cesium carbonate; diethylamine, ammonia, pyrrolidine, piperidine, aniline, methylaniline, triethylamine, lithium diisopropylamide, sodium amide, etc. Nitrogen-containing bases; organic alkali metal compounds such as butyl lithium, methyl lithium, and phenyl lithium; methyl magnesium chloride, methyl magnesium bromide, phenyl magne Grignard reagents such Umukurorido like.

In the reaction [B], a solvent may be used as necessary. Although there is no restriction | limiting in particular in the solvent to be used, The solvent similar to reaction [A] is mentioned.
In order to carry out the reaction more efficiently in the reaction [B], a catalyst may be used. As the catalyst, a known catalyst can be used as an anti-dense catalyst that reacts a compound having an HN bond with a compound represented by RX to form an RN bond, and in particular, transition metals represented by palladium and nickel The catalyst is effective. When these catalysts are used, a metal salt and a ligand can be used in combination, or a ligand in which a ligand is previously coordinated to a transition metal atom may be used. Examples of the metal salt include palladium chloride, palladium acetate, tris (benzylideneacetone) dipalladium, nickel chloride and the like. As ligands that react with these metal salts to improve catalytic activity, triphenylphosphine, tri (t-butyl) phosphine, tri (t-butyl) phosphine / tetrafluoroborate, tricyclohexylphosphine, tricyclohexylphosphine / Examples thereof include phosphines such as tetrafluoroborate, tri (o-tolyl) phosphine, bis (diphenylphosphino) ferrocene, and dialkylbiarylphosphines (Buckwald ligand).

The reaction temperature of the reactions [A] and [B] is not particularly limited, but is preferably -100 to 300 ° C, more preferably -40 to 150 ° C.
Next, an example of a method for producing the fluorene compound [I ′] according to the present invention will be described.
The fluorene compound [I ′] is represented by the following formula:

（R³〜R¹⁶は、それぞれ前記一般式[I']における同一記号と同義であり、Lは、後述する（〔遷移金属化合物[II]の製造方法〕に記載する）式[D]および[E]における同一記号と同義である。）
で表される化合物である場合には、この化合物(5)はフルオレン化合物[I]であって一般式[I]においてR¹およびR²が水素原子である化合物を原料として、後述する、前駆体化合物（1）からジアルカリ金属塩を合成する方法と同様の方法を利用して製造することができる。すなわち、フルオレン化合物[I]と、アルカリ金属、水素化アルカリ金属、アルカリ金属アルコキシド、有機アルカリ金属および有機アルカリ土類金属から選ばれる少なくとも１種の金属成分とを有機溶媒中で接触させることで、両者の反応を行い、化合物(5)が製造される。
また、フルオレン化合物[I']が下記式：

(R ^{3 to} R ¹⁶ are respectively synonymous with the same symbols in the general formula [I ′], and L represents a formula [D] and a formula (described in [Production Method of Transition Metal Compound [II]) described later] (It is synonymous with the same symbol in [E].)
In this case, the compound (5) is a fluorene compound [I], and a compound in which R ¹ and R ² are hydrogen atoms in the general formula [I] is used as a raw material. It can be produced using a method similar to the method of synthesizing a dialkali metal salt from the body compound (1). That is, by contacting the fluorene compound [I] with at least one metal component selected from an alkali metal, an alkali metal hydride, an alkali metal alkoxide, an organic alkali metal and an organic alkaline earth metal in an organic solvent, Both compounds are reacted to produce compound (5).
In addition, the fluorene compound [I ′] has the following formula:

（R³〜R¹⁶は、それぞれ前記一般式[I']における同一記号と同義であり、Aは窒素原子またはリン原子であり、R¹⁷、R¹⁸およびR²³は、それぞれ独立に、水素原子ならびに上述した炭化水素基、ケイ素含有基、ヘテロ原子含有炭化水素基から選ばれる置換基であり、Y、M、Qおよびjは、それぞれ前記一般式[II]における同一記号と同義である。）
で表される化合物(10a)である場合には、この化合物(10a)を製造する過程では、まず、上述のフルオレン化合物[I]を用いて、例えば以下に示す反応[C]で表されるような経路を経てその前駆体である化合物（10）が製造される（例えばJ. AM. CHEM. SOC., 126, 16716-16717,(2004)）。

(R ^{3 to} R ¹⁶ are respectively synonymous with the same symbol in the general formula [I ′], A is a nitrogen atom or a phosphorus atom, R ¹⁷ , R ¹⁸ and R ²³ are each independently a hydrogen atom. And a substituent selected from the above-described hydrocarbon group, silicon-containing group, and heteroatom-containing hydrocarbon group, and Y, M, Q, and j are respectively synonymous with the same symbols in general formula [II].)
In the process of producing this compound (10a), first, using the above-mentioned fluorene compound [I], for example, represented by the reaction [C] shown below Through such a route, the precursor compound (10) is produced (for example, J. AM. CHEM. SOC., 126, 16716-16717, (2004)).

ここでXは後述する[E]における同一記号と同義である。

Here, X is synonymous with the same symbol in [E] described later.

As reaction conditions, the same conditions as those employed in the method described later (described in [Method for producing transition metal compound [II]]) may be employed.
Compound (10) can be converted to a dialkali metal salt by the method described later (described in [Production Method of Transition Metal Compound [II])), and further to a fluorene compound having a metal-containing group. That is, by bringing compound (10) into contact with at least one metal component selected from an alkali metal, an alkali metal hydride, an alkali metal alkoxide, an organic alkali metal and an organic alkaline earth metal in an organic solvent, To produce a dialkali metal salt of compound (10), and this dialkali metal salt and the following general formula [III]:
MQ _{j + 2} … [III]
(In the formula, M, Q and j have the same meanings as those in the formula (10a)).
Is reacted with an organic solvent to produce a compound (10a) which is a fluorene compound having a metal-containing group.

[Production Method of Transition Metal Compound [II]]
The transition metal compound [II] according to the present invention can be produced by using a known method, and the production method is not particularly limited. Below, the example of the manufacturing method of transition metal compound [II] used by this invention is demonstrated. First, a method for producing intermediate (1), which is a precursor of transition metal compound [II], will be described, and then a method for producing dialkali metal salt and a method for producing transition metal compound [II] will be described in this order.

<Precursor synthesis>

上記式[D]中、R³〜R²²はそれぞれ一般式[II]中の同一記号と同義であり、Yは炭素原子である。上記式[E]中、R³〜R²²はそれぞれ一般式[II]中の同一記号と同義であり、Yはケイ素原子、Xはフッ素、塩素、臭素、ヨウ素等のハロゲンの原子、メトキシ基、エトキシ基、イソポロポキシ基などのアルコキシ基、ジメチルアミノ基、ジエチルアミノ基などのアミノ基、またはトリフレート基である。

In the above formula [D], R ^{3 to} R ²² are each synonymous with the same symbol in general formula [II], and Y is a carbon atom. In the above formula [E], R ^{3 to} R ²² are respectively synonymous with the same symbols in the general formula [II], Y is a silicon atom, X is a halogen atom such as fluorine, chlorine, bromine and iodine, and a methoxy group , An alkoxy group such as an ethoxy group and an isoporoxy group, an amino group such as a dimethylamino group and a diethylamino group, or a triflate group.

  In the above formulas [D] and [E], L is an alkali metal atom, an alkaline earth metal atom or an alkaline earth metal salt. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of the alkaline earth metal salt include magnesium chloride (MgCl) and magnesium bromide. (MgBr), magnesium iodide (MgI), butyl magnesium (BuMg), calcium chloride (CaCl).

  In the precursor compound (1) represented by the above formula (1), it is possible to consider the presence of isomers having different positions of double bonds in the cyclopentadienyl ring. In the above formulas [D] and [E] Are only one of them, but the precursor compound (1) may be other isomers having different double bond positions in the cyclopentadienyl ring, or a mixture thereof. You may use for a process. The precursor compound (1) includes all optical isomers that can be constituted by the compound represented by the above formula (1) and other isomers having different positions of double bonds in the cyclopentadienyl ring, A mixture thereof may be used.

  As the method for synthesizing the fulvene compound (4) from the cyclopentadiene compound (2) and the carbonyl compound (3) in the formula [D], a known method can be used. In this reaction, a base may be used in combination, and examples of the base include those that can be used in the above-mentioned reaction [B]. Two or more bases may be used in combination. When a base is used in combination, the cyclopentadiene compound (2) may be reacted with the base in advance and then reacted with the carbonyl compound (3), or the cyclopentadiene compound (2), the carbonyl compound (3) and the base may be reacted. You may make it react simultaneously, and can make a base react in arbitrary orders. In order to accelerate the reaction, a Lewis base such as an amine compound, an amide compound, or an imide compound, or a Lewis acid can be used. Examples of the Lewis base include N, N′-tetramethylethylenediamine, 1-methylimidazole, N, N′-dimethylimidazolidinone, and examples of the Lewis acid include boron trifluoride, magnesium chloride, magnesium bromide, Examples include zinc chloride.

  In the formulas [D] and [E], the compound (5) can be produced by the above-described method, and the compound (11) is the same as the method for synthesizing a dialkali metal salt from the precursor compound (1) described later. It can manufacture using the method of. That is, the following general formula:

（R¹⁹〜R²²は、それぞれ一般式[II]における同一記号と同義である。）
で表される化合物（該化合物は、二重結合の位置が違うすべての異性体を包含し、これらの混合物であっても良い。）と、アルカリ金属、水素化アルカリ金属、アルカリ金属アルコキシド、有機アルカリ金属および有機アルカリ土類金属から選ばれる少なくとも１種の金属成分とを有機溶媒中で接触させることで、両者の反応を行い、化合物(11)が製造される。

(R ^{19 to} R ²² are each synonymous with the same symbol in general formula [II].)
A compound represented by the formula (this compound includes all isomers having different double bond positions, and may be a mixture thereof), alkali metal, alkali metal hydride, alkali metal alkoxide, organic By contacting at least one metal component selected from an alkali metal and an organic alkaline earth metal in an organic solvent, both are reacted to produce compound (11).

Examples of the organic solvent that can be used in the reaction represented by the above formula [D] or [E] include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; benzene, toluene, xylene, and the like. Aromatic hydrocarbons; tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, cyclopentyl methyl ether, and other ethers; dichloromethane, chloroform, and other halogenated hydrocarbons; and two or more of these The solvent obtained by mixing is mentioned.
The reaction temperature is preferably -100 to 150 ° C, more preferably -40 to 120 ° C.

<Synthesis of dialkali metal salt>
By bringing the precursor compound (1) into contact with at least one metal component selected from an alkali metal, an alkali metal hydride, an alkali metal alkoxide, an organic alkali metal and an organic alkaline earth metal in an organic solvent, To obtain a dialkali metal salt.

  Examples of the alkali metal that can be used in the above reaction include lithium, sodium, and potassium; examples of the alkali metal hydride include sodium hydride and potassium hydride; and examples of the alkali metal alkoxide include sodium methoxide. , Potassium ethoxide, sodium ethoxide, potassium tert-butoxide, etc .; examples of the organic alkali metal include methyl lithium, butyl lithium, and phenyl lithium; examples of the organic alkaline earth metal include methyl magnesium halide, Examples thereof include butyl magnesium halide and phenyl magnesium halide. These may be used alone or in combination of two or more.

  Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, diethyl ether, dioxane, 1, 2 -Ethers such as dimethoxyethane, tert-butyl methyl ether and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; and solvents obtained by mixing two or more of these.

  The reaction between the precursor compound (1) and the metal component is preferably a molar ratio (precursor compound (1): metal component) = 1: 1 to 1:20, more preferably 1: 1.5 to 1: 4, particularly preferably from 1: 1.8 to 1: 2.5. The reaction temperature is preferably -100 to 200 ° C, more preferably -80 to 120 ° C.

  In order to promote the above reaction, Lewis bases such as tetramethylethylenediamine and α-methylstyrene as described in International Publication No. 2009/072505 can also be used.

<Synthesis of transition metal compound [II]>
The transition metal compound [II] is synthesized by reacting the dialkali metal salt obtained by the above reaction with the compound [III] represented by the following general formula [III] in an organic solvent.
MQ _{j + 2} … [III]
In the formula [III], M is a Group 4 transition metal, and a plurality of Qs are each independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. , J is an integer of 1 to 4. The atoms or groups listed as M and Q are the same as the atoms or groups listed as M and Q in the general formula [II], respectively.

  Examples of the compound [III] include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide; tetravalent zirconium fluoride, chloride, bromide and iodide; tetravalent hafnium fluoride, chloride. Products, bromides and iodides; and complexes of these with ethers such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane.

  Examples of the organic solvent used in the above reaction include the organic solvents described in the section <Synthesis of dialkali metal salt>. The reaction between the dialkali metal salt and compound [III] is preferably carried out at a molar ratio of 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1.2. The reaction temperature is preferably -80 to 200 ° C, more preferably -75 to 120 ° C.

<Other methods for producing transition metal compound [II]>
As another production method of the transition metal compound [II], the precursor compound (1) is converted into an organometallic reagent such as tetrabenzyl titanium, tetrabenzyl zirconium, tetrabenzyl hafnium, tetrakis (trimethylsilylmethylene) titanium, tetrakis (trimethylsilylmethylene). Examples of the production method include obtaining a transition metal compound [II] by directly reacting with zirconium, tetrakis (trimethylsilylmethylene) hafnium, dibenzyldichlorotitanium, dibenzyldichlorozirconium or dibenzyldichlorohafnium, or an amide salt of titanium, zirconium or hafnium. It is done.

The transition metal compound [II] obtained by these production methods can be isolated and purified by methods such as extraction, recrystallization and sublimation. The transition metal compound [II] obtained by such a method is identified by using analytical methods such as proton nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum, mass spectrometry, X-ray single crystal structure analysis and elemental analysis. Is done.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention contains a transition metal compound [II] represented by the general formula [II] (hereinafter also referred to as “transition metal compound (A)”).

The olefin polymerization catalyst according to the present invention further reacts with (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound (A). It is preferable to contain at least one compound selected from compounds that form ion pairs (hereinafter also referred to as “compound (B)”). The olefin polymerization catalyst according to the present invention may further contain (C) a carrier, if necessary. The olefin polymerization catalyst according to the present invention may further contain (D) an organic compound component, if necessary.
Hereinafter, each component other than the transition metal compound (A) will be specifically described.

<Compound (B)>
<< Organic metal compound (B-1) >>
Examples of the organometallic compound (B-1) include an organoaluminum compound (B-1a) represented by the following general formula (B-1a) and a Group 1 metal represented by the following general formula (B-1b) Group 1 and 2 such as complex alkylated product of B and aluminum (B-1b), group 2 or group 12 metal dialkyl compound (B-1c) represented by the following general formula (B-1c) Examples include organometallic compounds of Groups 12 and 13.

(B-1a): Ra _m Al (ORb) _n H _p X _q
In formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, p is a number satisfying 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum. .

(B-1b): M2AlRa ₄
In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(B-1c): RaRbM3
In formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethyl magnesium, diethyl magnesium, di n-butyl magnesium, ethyl n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di n-butyl zinc and diphenyl zinc. Of the organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred. An organometallic compound (B-1) may be used individually by 1 type, and may use 2 or more types together.
Of the above compounds, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride are particularly preferable because they are easily available and inexpensive.

《Organic aluminum oxy compound (B-2)》
The organoaluminum oxy compound (B-2) may be, for example, a conventionally known aluminoxane, and is insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. It may be. Specifically, as the organoaluminum oxy compound (B-2), a general formula:

または一般式：

Or general formula:

（式中、Ｒは炭素数１から１０の炭化水素基、nは2以上の整数を示す）
で表わされる化合物を挙げることができ、特にＲがメチル基及び／またはイソブチル基であるメチルアルミノキサンであってnが3以上、好ましくは5以上のものが利用される。これらアルミノキサン類に若干の有機アルミニウム化合物が混入していても差し支えない。

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more)
In particular, a methylaluminoxane in which R is a methyl group and / or isobutyl group and n is 3 or more, preferably 5 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds.

A conventionally well-known aluminoxane can be manufactured by the method of following (1)-(4), for example, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Adsorbed water-containing compounds or crystal water-containing salts, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium such as trialkylaluminum.

  (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

  (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  (4) Non-hydrolyzable compounds such as pyrolysis reactions produced by reacting organic aluminum such as trialkylaluminum with organic compounds having carbon-oxygen bonds such as tertiary alcohols, ketones, and carboxylic acids. How to convert.

  The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound (B-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.

In addition, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxane. Modified methylaluminoxane is an aluminoxane prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound is generally called MMAO. MMAO is a U.S. Patent No. 4
It can be prepared by the methods listed in 960878 and U.S. Pat. No. 5,041,584. In addition, Tosoh Finechem Co., Ltd. and the like have been commercially produced under the names MMAO and TMAO, which are prepared using trimethylaluminum and triisobutylaluminum and in which R is an isobutyl group.

  Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike MMAO, which is insoluble or hardly soluble in benzene, it is an aliphatic hydrocarbon. It has the feature of dissolving in alicyclic hydrocarbons.

  Further, as the organoaluminum oxy compound (B-2), for example, an organoaluminum oxy compound containing a boron atom and halogens exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010 can be used. Examples of the aluminoxane include ionic aluminoxane as exemplified in International Publication No. 2003/082879. A compound (B-2) may be used individually by 1 type, and may use 2 or more types together.

<Compound that reacts with transition metal compound (A) to form ion pair (B-3)>
As the compound (B-3) (hereinafter also referred to as “ionic compound (B-3)”) which reacts with the transition metal compound (A) to form an ion pair, for example, JP-A-1-501950 JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in 1). Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
As the ionic compound (B-3), a compound represented by the following general formula (B-3a) is preferable.

式（B-3a）中、R^e+としては、例えば、H⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが挙げられる。R^f〜Rⁱはそれぞれ独立に有機基であり、好ましくはアリール基である。

In formula (B-3a), examples of R ^{e +} include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{f to} R ⁱ are each independently an organic group, preferably an aryl group.

  Examples of the carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.

  Examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; N N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation And dialkyl ammonium cations.

  Examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tris (methylphenyl) phosphonium cation, and a tris (dimethylphenyl) phosphonium cation.

As R ^{e +} , for example, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Examples of the compound represented by the general formula (B-3a) include carbenium salts, ammonium salts, trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

  Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl). ) Carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o- Tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) Ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethyl Ammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4 -Dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-tri Fluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, dioctadecylmethylammonium.

  Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenyl borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoro Methylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.

  Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

As the ionic compound (B-2), an ionic compound disclosed by the present applicant (eg, Japanese Patent Application Laid-Open No. 2004-51676) can also be used without limitation.
An ionic compound (B-2) may be used individually by 1 type, and may use 2 or more types together.

  Among the above, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) are easy to obtain and inexpensive. Borate is particularly preferred.

<Carrier (C)>
Examples of the carrier (C) include inorganic or organic compounds and granular or fine particle solids. The transition metal compound (A) is preferably used in a form supported on the carrier (C).

<Inorganic compounds>
The inorganic compound in the carrier (C) is preferably a porous oxide, inorganic chloride, clay, clay mineral, or ion-exchangeable layered compound.

Examples of the porous oxide include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or composites containing these, the mixture can be used, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO ₂ —TiO ₂ —MgO can be used. Among these, a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable.

The properties of porous oxides vary depending on the type and production method. The carrier preferably used in the present invention has a particle size of preferably 1 to 300 μm, more preferably 3 to 100 μm; a specific surface area of preferably 50 to 1300 m ² / g, more preferably 200 to 1200 m ² / g. The pore volume is preferably 0.3 to 3.0 cm ³ / g, more preferably 0.5 to 2.0 cm ³ / g. Such a carrier is used after being dried and / or calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. The particle shape is not particularly limited, but is particularly preferably spherical.

As the inorganic chloride, for example, MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ are used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving inorganic chloride in solvent, such as alcohol, what was made to precipitate into a fine particle form with a depositing agent can also be used.

Clay is usually composed mainly of clay minerals. An ion-exchange layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Also, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, or ion crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

  Examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, pectolite, teniolite.

Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ- Examples include crystalline acidic salts of polyvalent metals such as Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like.

  The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Introducing another substance (also referred to as a “guest compound”) between the layered compounds in this way is called intercalation.

Examples of guest compounds include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ (R is Hydrocarbon groups, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ It is done. These compounds may be used individually by 1 type, and may use 2 or more types together. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _{2, and the} like can also coexist.

Examples of the pillar include an oxide generated by heat dehydrating after intercalating the metal hydroxide ions between layers.
Among the supports (C), a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable. Also preferred are clays or clay minerals, particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic ummo.

《Organic compound》
Examples of the organic compound in the carrier (C) include granular or fine particle solids having a particle size in the range of 5 to 300 μm. Specifically, the main components are (co) polymers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and other α-olefins having 2 to 14 carbon atoms, vinylcyclohexane and styrene. The (co) polymer produced | generated as a component, and those modifications can be illustrated.

<Organic compound component (D)>
In the present invention, the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

<Usage and order of addition of each component>
In the method for producing an olefin polymer according to the present invention, the usage of each component and the order of addition are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound (A), the compound (B), the carrier (C) and the organic compound component (D) are also referred to as “components (A) to (D)”, respectively.
(1) A method in which component (A) is added alone to the polymerization vessel.
(2) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (A) supported on component (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component carrying the component (B) on the component (C) and the component (A) are added to the polymerization vessel in an arbitrary order.
(5) A method in which a catalyst component in which component (A) and component (B) are supported on component (C) is added to the polymerization vessel.

  In each of the above methods (1) to (5), the component (D) may be added in any order as necessary. Moreover, at least 2 types of each catalyst component may be contacted previously. In each of the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the component (B) may be the same or different. In addition, the solid catalyst component in which the component (C) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In addition, a catalyst component may be further supported on the prepolymerized solid catalyst component. Further, the component (D) may be supported as necessary.

[Olefin polymer production method]
The method for producing an olefin polymer according to the present invention includes a step of polymerizing one or more olefins selected from ethylene and an α-olefin having 3 to 30 carbon atoms in the presence of the above-mentioned catalyst for olefin polymerization. At least one of the olefins is ethylene or propylene. Here, the term “polymerization” is used to collectively refer to homopolymerization and copolymerization. In addition, “polymerize olefin in the presence of olefin polymerization catalyst” means that each component of the olefin polymerization catalyst can be added to the polymerization vessel by any method as in the above methods (1) to (5). It includes embodiments that polymerize olefins.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may implement what is called bulk polymerization method using the liquefied olefin itself which can be supplied to superposition | polymerization as a solvent.

  When the olefin polymerization is performed using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows. In the olefin polymerization catalyst, the content of each component can be adjusted as follows.

Component (A) is generally used in an amount of 10 ⁻¹⁰ to 10 ⁻² mol, preferably 10 ⁻⁸ to 10 ⁻³ mol, per liter of reaction volume. The organometallic compound (B-1) (hereinafter also referred to as “component (B-1)”) is a molar ratio of the component (B-1) to the total transition metal atom (M) in the component (A) [( B-1) / M] is usually 1 to 50,000, preferably 10 to 20,000, particularly preferably 15 to 10,000. The organoaluminum oxy compound (B-2) (hereinafter also referred to as “component (B-2)”) consists of an aluminum atom in component (B-2) and all transition metal atoms (M) in component (A). The molar ratio [Al / M] is usually 10 to 5,000, preferably 20 to 2,000. The ionic compound (B-3) (hereinafter also referred to as “component (B-3)”) has a molar ratio [(B-3) to the total transition metal atom (M) in the component (A) [( B-3) / M] is usually 1 to 1000, preferably 1 to 200, particularly preferably 1 to 20.

  When component (C) is used, the weight ratio [(A) / (C)] of component (A) to component (C) is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and still more preferably 0.001 to It can be used in such an amount that it becomes 0.1.

  When component (D) is used, when component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. When the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. When component (B) is component (B-3), the molar ratio (D) / (B-3)] is usually 0.01-10, preferably 0.1-5. it can.

  In the production method of the present invention, the polymerization temperature of the olefin is usually −50 to + 250 ° C., preferably 0 to 200 ° C .; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. is there. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen or the like to be present in the polymerization system, changing the polymerization temperature, or using the component (B).

  The production method of the present invention can produce an olefin polymer having a high molecular weight while maintaining high catalytic activity even under high temperature conditions advantageous in an industrial production method. Under such high temperature conditions, the polymerization temperature is usually 40 ° C. or higher, preferably 40 to 250 ° C., more preferably 45 to 220 ° C., particularly preferably 50 to 200 ° C. (in other words, particularly preferably industrializable. Temperature.).

  In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.

  For the olefin polymer obtained by the production method of the present invention, after synthesis by the above method, a post-treatment step such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary. It's okay.

<Olefin>
In the production method of the present invention, the olefin supplied to the polymerization reaction is at least one olefin selected from ethylene and an α-olefin having 3 to 30 carbon atoms, and includes at least ethylene and / or propylene.

  As the α-olefin, an α-olefin having 3 to 20 carbon atoms is more preferable, and an α-olefin having 3 to 10 carbon atoms is particularly preferable. Examples of α-olefins include linear or branched α-olefins. Examples of linear or branched α-olefins include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icocene.

  Moreover, at least 1 sort (s) chosen from the cyclic olefin, the monomer which has a polar group, a terminal hydroxylated vinyl compound, and an aromatic vinyl compound can coexist in a reaction system, and polymerization can also be advanced. It is also possible to use polyene in combination. Further, other components such as vinylcyclohexane may be copolymerized without departing from the spirit of the present invention.

  Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

  Examples of the monomer having a polar group include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Α, β-unsaturated carboxylic acids such as products, and metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt, aluminum salt; methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-butyl and isobutyl methacrylate; vinyl acetate, Vinyl esters such as vinyl ropionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate It is done.

  Examples of the terminal hydroxylated vinyl compound include hydroxide-1-butene, hydroxide-1-pentene, hydroxide-1-hexene, hydroxide-1-octene, hydroxide-1-decene, hydroxide-1- Linear terminal hydroxylated vinyl compounds such as undecene, hydroxide-1-dodecene, hydroxide-1-tetradecene, hydroxide-1-hexadecene, hydroxide-1-octadecene, hydroxide-1-eicocene; -3-methyl-1-butene, hydroxide-3-methyl-1-pentene, hydroxide-4-methyl-1-pentene, hydroxide-3-ethyl-1-pentene, hydroxide-4,4-dimethyl hydroxide -1-pentene, 4-methyl-1-hexene hydroxide, 4,4-dimethyl-1-hexene hydroxide, 4-ethyl-1-hexene hydroxide, 3-ethyl-1-hexene hydroxide And branched terminal hydroxylated vinyl compounds.

  As the aromatic vinyl compound, for example, styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, etc. Alternatively, polyalkylstyrene; methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene and other functional group-containing styrene derivatives; 3-phenyl Examples include propylene, 4-phenylpropylene, and α-methylstyrene.

  The polyene is preferably selected from dienes and trienes. It is also a preferred embodiment that polyene is used within a range of 0.0001 to 50 mol%, and a more preferred embodiment is used within a range of 0.0001 to 10 mol%, based on the total olefin supplied to the polymerization reaction.

  Examples of the dienes include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1, Α, ω-unconjugated dienes such as 9-decadiene; 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl Non-conjugated dienes such as -1,7-nonadiene; conjugated dienes such as butadiene and isoprene. Among these, α, ω-nonconjugated dienes and dienes having a norbornene skeleton are preferable.

  Examples of the triene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4- Ethylidene-1,6, -octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1, 6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7- Nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecane Nonconjugated trienes such as ene; include trienes such as 1,3,5-hexatriene. Among these, non-conjugated triene having a double bond at the terminal, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND) is preferable.

  Each of the diene and triene may be used alone or in combination of two or more. A combination of diene and triene may also be used. Among the polyenes, α, ω-nonconjugated dienes and polyenes having a norbornene skeleton are particularly preferable.

  In the method for producing an olefin polymer of the present invention, it is more preferable that at least one of the supplied olefins is ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Preferably, ethylene and propylene are more preferable, and polymerization is also preferably performed in the presence of polyene, ethylene homopolymerization, ethylene / propylene copolymerization, ethylene / 1-butene copolymerization, ethylene / 1-hexene copolymerization, Particularly preferred are ethylene / 1-octene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, propylene homopolymer, propylene / 1-butene copolymer and 1-butene homopolymer.

  The ethylene / α-olefin copolymer produced by the production method of the present invention is derived from (i) a structural unit (ethylene unit) derived from ethylene and (ii) an α-olefin having 3 to 30 carbon atoms. The structural unit (α-olefin unit) is usually expressed in a molar ratio [(i) / (ii)] in the range of 99/1 to 1/99, but is not particularly limited.

  The proportion of the structural unit derived from polyene in the ethylene / α-olefin / polyene copolymer produced by the production method of the present invention is not particularly limited, but is usually 0.1 to 50 mol%, preferably in all structural units. Is in the range of 0.2 to 15 mol%, more preferably 0.3 to 12 mol%.

  The polystyrene-reduced weight average molecular weight measured by GPC of the olefin polymer produced by the production method of the present invention is not particularly limited, but is usually in the range of 10000 to 5000000, preferably 50000 to 2000000. When the weight average molecular weight is within the range, it is preferable from the viewpoint of excellent molding processability.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the olefin polymer obtained by the method for producing an olefin polymer of the present invention is 1.0 to 5.0, preferably It is 1.2 to 4.5, more preferably 1.5 to 4.1, but there is no particular limitation.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Measurement methods for various physical properties]
Weight average molecular weight (Mw), number average molecular weight (Mn)
Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) using Waters Alliance GPC2000 by moving 500 μl of 0.15 (w / v) concentration sample solution at a flow rate of 1.0 ml / min. Went. Standard polystyrene was manufactured by Tosoh Corporation, and the molecular weight in terms of polystyrene was calculated.
Separation columns: TSKgel GMH6-HT and TSKgel GMH6-HTL (2 columns each having an inner diameter of 7.5 mm and a length of 300 mm were used.)
・ Column temperature: 140 ℃
・ Mobile phase: o-dichlorobenzene (containing 0.025wt% dibutylhydroxytoluene)
・ Detector: Differential refractometer

The ethylene content of the copolymer and the ethylene content and ENB content of the ENB content copolymer were calculated from ¹ H-NMR spectra. ¹ H-NMR spectrum was obtained by dissolving 20 mg of sample in 0.6 ml of deuterated o-dichlorobenzene, using ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL, 120 ° C, 45 degree pulse, repetition time 7 seconds. The measurement was made at 512 times. The standard value for chemical shift was 1.20 ppm for the main chain methylene signal of the copolymer. The 5.55-5.35ppm peak is derived from disubstituted internal olefin (2H), the 5.35-4.80ppm peak is derived from ENB-derived vinylidene group (1H), the 4.80-4.55ppm peak is derived from vinylidene group (1H), and 0.91-0.10ppm is derived from propylene The methyl group and the peak of 3.50-0.91 ppm were regarded as peaks derived from other protons, and the content was calculated from the respective area ratios.

Identification of the structure and purity of the compound and catalyst The structure and purity of the compound and catalyst obtained in Examples, etc. are measured by nuclear magnetic resonance (NMR, GSH-270 manufactured by JEOL Ltd.), electrolytic desorption mass spectrometry (FD-MS, SX-102A manufactured by JEOL Ltd.), single crystal X-ray structure analysis (D8 VENTURE, Cu source manufactured by Bruker AXS Co., Ltd.) and the like. In nuclear magnetic resonance using deuterated toluene as a solvent, the spectrum previously measured only with deuterated toluene was subtracted, and the signal derived from ¹ H remaining in deuterated toluene was erased, and assignment was performed. As for the single crystal X-ray structural analysis results, an ORTEP diagram (50% probability) excluding hydrogen atoms is shown.

Unless otherwise specified, all Examples and Comparative Examples were performed using a dry solvent under a dry nitrogen atmosphere.
In the figure, when there are a plurality of isomers with respect to the double bond position of the cyclopentadiene ring, only one isomer is shown.

[Synthesis of fluorene compounds]
[Example 1A]
Synthesis of fluorene compound A

窒素雰囲気下、100ml 3つ口フラスコに2,7-ジアミノフルオレン5.00g(25.5mmol)、ヨウ素0.660g(2.60mmol)、脱水アセトン37.19gを装入した。還流下で17時間反応させた後、減圧下で濃縮した。トルエンを加え、再度濃縮した。アミノ化シリカゲルを用いたクロマトグラフィーにより精製し、アセトンとヘキサンの混合溶媒から再結晶することにより、上記式[1A]で表される化合物（以下「フルオレン化合物A」という。）を得た。収量2.98g、収率32％であった。
¹H-NMRおよび単結晶X線構造解析により同定を行った。
¹H-NMR (CD₃CN) δ: 7.35 (2H, s), 6.58 (2H, s), 5.34 (2H, s), 4.47 (2H, br s), 3.63 (2H, s), 2.04 (6H, d, J = 1.6 Hz), 1.23 (12H, s).

Under a nitrogen atmosphere, a 100 ml three-necked flask was charged with 5.00 g (25.5 mmol) of 2,7-diaminofluorene, 0.660 g (2.60 mmol) of iodine, and 37.19 g of dehydrated acetone. The mixture was reacted for 17 hours under reflux, and then concentrated under reduced pressure. Toluene was added and concentrated again. Purification by chromatography using aminated silica gel and recrystallization from a mixed solvent of acetone and hexane gave a compound represented by the above formula [1A] (hereinafter referred to as “fluorene compound A”). The yield was 2.98 g and the yield was 32%.
Identification was performed by ¹ H-NMR and single crystal X-ray structural analysis.
¹ H-NMR (CD ₃ CN) δ: 7.35 (2H, s), 6.58 (2H, s), 5.34 (2H, s), 4.47 (2H, br s), 3.63 (2H, s), 2.04 (6H , d, J = 1.6 Hz), 1.23 (12H, s).

[Example 1B]
Synthesis of fluorene compound B

窒素雰囲気下、50ml ギルダールフラスコに実施例1Aで製造されたフルオレン化合物A 1.01g(2.83mmol)、炭酸カリウム0.931g(6.74mmol)、脱水アセトニトリル20.40g、ヨウ化メチル2.40g(16.9mmol)を装入した。これらを、60℃で18時間反応させた後、減圧下で濃縮した。トルエンを加え、水及び飽和塩化ナトリウム水溶液で洗浄した。アミノ化シリカゲルを用いたクロマトグラフィーにより精製し、ヘキサンで洗浄することにより、上記式[1B]で表される化合物（以下「フルオレン化合物B」という。）を得た。収量0.315g、収率29％であった。
¹H-NMRおよびFD-MSにより同定を行った。
¹H-NMR (Toluene-d₈) δ: 7.54 (2H, s), 6.68 (2H, s), 5.15 (2H, d, J = 1.3 Hz), 3.73 (2H, s), 2.60 (6H, s), 1.97 (6H, d, J = 1.3 Hz), 1.17 (12H, s).
FD-MS m/z=384.3

Under a nitrogen atmosphere, 1.01 g (2.83 mmol) of the fluorene compound A prepared in Example 1A, 0.931 g (6.74 mmol) of potassium carbonate, 20.40 g of dehydrated acetonitrile and 2.40 g of methyl iodide (16.9 mmol) were prepared in a 50 ml Gildar flask. I was charged. These were reacted at 60 ° C. for 18 hours and then concentrated under reduced pressure. Toluene was added and washed with water and saturated aqueous sodium chloride solution. Purification by chromatography using aminated silica gel and washing with hexane gave a compound represented by the above formula [1B] (hereinafter referred to as “fluorene compound B”). The yield was 0.315 g and the yield was 29%.
Identification was performed by ¹ H-NMR and FD-MS.
¹ H-NMR (Toluene-d ₈ ) δ: 7.54 (2H, s), 6.68 (2H, s), 5.15 (2H, d, J = 1.3 Hz), 3.73 (2H, s), 2.60 (6H, s ), 1.97 (6H, d, J = 1.3 Hz), 1.17 (12H, s).
FD-MS m / z = 384.3

[Example 1C]
Synthesis of fluorene compound C

窒素雰囲気下、50ml ギルダールフラスコに実施例1Aで製造されたフルオレン化合物A 1.51g(4.22mmol)、炭酸カリウム1.46g(10.6mmol)、脱水アセトニトリル20.00g、ヨウ化エチル6.59g(42.2mmol)を装入した。これらを、70℃で23時間反応させた後、トルエンを加え、水で洗浄した。硫酸マグネシウムで乾燥後、アミノ化シリカゲルを用いたクロマトグラフィーにより精製し、メタノールで洗浄することにより、上記式[1C]で表される化合物（以下「フルオレン化合物C」という。）を得た。収量1.47g、収率84％であった。
¹H-NMRおよびFD-MSにより同定を行った。
¹H-NMR (Toluene-d₈) δ: 7.54 (2H, s), 6.71 (2H, s), 5.08 (2H, d, J = 1.3 Hz), 3.73 (2H, s), 3.13 (4H, q, J = 7.0 Hz), 1.96 (6H, d, J = 1.3 Hz), 1.18 (12H, s), 1.08 (7H, t, J = 7.0 Hz).
FD-MS m/z=412.3

Under a nitrogen atmosphere, 1.51 g (4.22 mmol) of the fluorene compound A prepared in Example 1A, 1.46 g (10.6 mmol) of potassium carbonate, 20.00 g of dehydrated acetonitrile, and 6.59 g (42.2 mmol) of ethyl iodide in a 50 ml Gildar flask. I was charged. These were reacted at 70 ° C. for 23 hours, and then toluene was added and washed with water. After drying over magnesium sulfate, the product was purified by chromatography using aminated silica gel and washed with methanol to obtain a compound represented by the above formula [1C] (hereinafter referred to as “fluorene compound C”). The yield was 1.47 g and the yield was 84%.
Identification was performed by ¹ H-NMR and FD-MS.
¹ H-NMR (Toluene-d ₈ ) δ: 7.54 (2H, s), 6.71 (2H, s), 5.08 (2H, d, J = 1.3 Hz), 3.73 (2H, s), 3.13 (4H, q , J = 7.0 Hz), 1.96 (6H, d, J = 1.3 Hz), 1.18 (12H, s), 1.08 (7H, t, J = 7.0 Hz).
FD-MS m / z = 412.3

[Synthesis of transition metal compounds]
[Example 2A]
Synthesis of transition metal compound A (1) Synthesis of ligand A

窒素雰囲気下、30mlシュレンク管にtert-ブチルメチルエーテル20ml、フルオレン化合物B 0.279g（0.726mmol）を装入した。この溶液にn-ブチルリチウムのヘキサン溶液（1.65M、0.45ml、0.74mmol）を氷水浴下、10分かけて滴下した。室温で20時間撹拌した。特開2004-168774を参考に合成した6,6-ジ（4-メチルフェニル）フルベン0.200g(0.775mmol)を加え、室温で22時間撹拌した。反応溶液に水100ml及びトルエン200mlを装入し、有機層を分離し、飽和塩化ナトリウム水溶液で洗浄した。硫酸マグネシウムで乾燥後、シリカゲルカラムクロマトグラフィーによって精製し、ヘキサンおよびメタノールで洗浄することにより上記式[2A-1]で表される化合物（以下「配位子A」という。）を粉末として得た。収量0.164g、収率35％であった。
FD-MSの測定結果により、目的物を同定した。
FD-MS:m/Z=642.4(M⁺)

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 20 ml of tert-butyl methyl ether and 0.279 g (0.726 mmol) of fluorene compound B. To this solution, n-butyllithium in hexane (1.65M, 0.45 ml, 0.74 mmol) was added dropwise over 10 minutes in an ice-water bath. Stir at room temperature for 20 hours. 6,6-di (4-methylphenyl) fulvene 0.200 g (0.775 mmol) synthesized with reference to JP-A-2004-168774 was added, and the mixture was stirred at room temperature for 22 hours. The reaction solution was charged with 100 ml of water and 200 ml of toluene, and the organic layer was separated and washed with a saturated aqueous sodium chloride solution. After drying over magnesium sulfate, the product was purified by silica gel column chromatography and washed with hexane and methanol to obtain a compound represented by the above formula [2A-1] (hereinafter referred to as “ligand A”) as a powder. . The yield was 0.164 g and the yield was 35%.
The target product was identified from the FD-MS measurement results.
FD-MS: m / Z = 642.4 (M ⁺ )

(2) Synthesis of transition metal compound A

窒素雰囲気下、30mlシュレンク管に配位子A 0.165g（0.257mmol）、α-メチルスチレン0.0608g(0.515mmol)、シクロペンチルメチルエーテル0.256gを装入した。1.60Mのn-ブチルリチウムヘキサン溶液0.33ml（0.53mmol）を6分間で滴下した。60℃に昇温後、4時間撹拌した。氷/アセトン浴で冷却後、系内を5min減圧し、窒素で常圧に戻した。四塩化ハフニウム0.0886g(0.277mmol)を加えた。室温で17時間反応させた。溶媒を留去し、得られた固体にトルエン20mlを加え、不溶物を濾過によって取り除いた。得られた溶液を濃縮し、ヘキサンを加えた。析出した固体を濾過によって取り出し、トルエンで洗浄し、上記式[2A-2]で表される目的物（以下「遷移金属化合物A」という。）を粉末として得た。収量0.130g、収率57％であった。
¹H-NMR、FD-MSの測定結果により、目的物を同定した。
¹H-NMR (Toluene-d₈) δ: 7.80 (2H, s), 7.74-7.66 (4H, m), 7.02-6.97 (2H, m), 6.94-6.90 (2H, m), 6.22 (2H, t, J = 2.8 Hz), 5.85(2H, t, J = 2.8 Hz), 5.46 (2H, s), 5.20 (2H, d, J = 1.0 Hz), 2.17 (6H, s), 2.10 (6H, s), 1.98 (6H, d, J = 1.5 Hz), 1.11 (6H, s), 1.07 (6H, s).
FD-MS m/z=890.3（M⁺）

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.165 g (0.257 mmol) of ligand A, 0.0608 g (0.515 mmol) of α-methylstyrene and 0.256 g of cyclopentylmethyl ether. 0.33 ml (0.53 mmol) of a 1.60M n-butyllithium hexane solution was added dropwise over 6 minutes. After raising the temperature to 60 ° C., the mixture was stirred for 4 hours. After cooling in an ice / acetone bath, the system was depressurized for 5 min and returned to normal pressure with nitrogen. 0.0886 g (0.277 mmol) of hafnium tetrachloride was added. The reaction was allowed to proceed for 17 hours at room temperature. The solvent was distilled off, 20 ml of toluene was added to the obtained solid, and insoluble matters were removed by filtration. The resulting solution was concentrated and hexane was added. The precipitated solid was taken out by filtration and washed with toluene to obtain the desired product represented by the above formula [2A-2] (hereinafter referred to as “transition metal compound A”) as a powder. The yield was 0.130 g and the yield was 57%.
^The target product was identified from the measurement results of ¹ H-NMR and FD-MS.
¹ H-NMR (Toluene-d ₈ ) δ: 7.80 (2H, s), 7.74-7.66 (4H, m), 7.02-6.97 (2H, m), 6.94-6.90 (2H, m), 6.22 (2H, t, J = 2.8 Hz), 5.85 (2H, t, J = 2.8 Hz), 5.46 (2H, s), 5.20 (2H, d, J = 1.0 Hz), 2.17 (6H, s), 2.10 (6H, s), 1.98 (6H, d, J = 1.5 Hz), 1.11 (6H, s), 1.07 (6H, s).
FD-MS m / z = 890.3 (M ⁺ )

[Example 2B]
Synthesis of transition metal compound B (1) Synthesis of ligand B

窒素雰囲気下、30mlシュレンク管にtert-ブチルメチルエーテル20ml、フルオレン化合物C 0.898g（2.18mmol）を装入した。この溶液にn-ブチルリチウムのヘキサン溶液（1.64M、1.38ml、2.26mmol）を氷水浴下、10分かけて滴下した。室温で16時間撹拌した。特開2004-168774を参考に合成した6,6-ジ（4-メチルフェニル）フルベン0.615g(2.38mmol)を加え、室温で25時間撹拌した。反応溶液に水100ml及びトルエン250mlを装入し、有機層を分離し、水、飽和塩化ナトリウム水溶液で洗浄した。硫酸マグネシウムで乾燥後、シリカゲルカラムクロマトグラフィーによって精製し、メタノール洗浄することにより上記式[2B-1]で表される化合物（以下「配位子B」という。）を粉末として得た。収量1.00g、収率69％であった。
FD-MSの測定結果により、目的物を同定した。
FD-MS:m/Z=670.4(M⁺)

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 20 ml of tert-butyl methyl ether and 0.898 g (2.18 mmol) of fluorene compound C. To this solution, a hexane solution of n-butyllithium (1.64M, 1.38 ml, 2.26 mmol) was added dropwise over 10 minutes in an ice-water bath. Stir at room temperature for 16 hours. 0.615 g (2.38 mmol) of 6,6-di (4-methylphenyl) fulvene synthesized with reference to JP-A-2004-168774 was added and stirred at room temperature for 25 hours. The reaction solution was charged with 100 ml of water and 250 ml of toluene, and the organic layer was separated and washed with water and a saturated aqueous sodium chloride solution. After drying over magnesium sulfate, the product was purified by silica gel column chromatography and washed with methanol to obtain a compound represented by the above formula [2B-1] (hereinafter referred to as “ligand B”) as a powder. The yield was 1.00 g and the yield was 69%.
The target product was identified from the FD-MS measurement results.
FD-MS: m / Z = 670.4 (M ⁺ )

  (2) Synthesis of transition metal compound B

窒素雰囲気下、30mlシュレンク管に配位子B 0.500g（0.745mmol）、α-メチルスチレン0.176g(1.49mmol)、シクロペンチルメチルエーテル0.744gを装入した。1.64Mのn-ブチルリチウムヘキサン溶液0.920ml（1.51mmol）を10分間で滴下した。60℃に昇温後、4時間撹拌した。氷/アセトン浴で冷却後、系内を5min減圧し、窒素で常圧に戻した。四塩化ハフニウム0.236g(0.736mmol)を加えた。室温で17時間反応させた。溶媒を留去し、得られた固体をヘキサンで洗浄後、トルエン150mlで可溶分を抽出し、不溶物を濾過によって取り除いた。得られた溶液を濃縮し、析出した固体を濾過によって取り出した。トルエンで洗浄し、上記式[2B-2]で表される目的物（以下「遷移金属化合物B」という。）を粉末として得た。収量0.520g、収率74％であった。
¹H-NMR、FD-MSの測定結果により、目的物を同定した。¹H-NMRによると、前記粉末はトルエンを4.3wt%含んでいた。
¹H-NMR (THF-d8) δ: 7.81-7.74 (4H, m), 7.64 (2H, s), 7.19-7.11 (4H, m), 6.21 (2H, t, J = 2.7 Hz), 5.68 (2H, t, J = 2.7 Hz), 5.34(2H, d, J = 1.3 Hz), 5.23 (2H, s), 2.93-2.70 (4H, m), 2.29 (6H, s), 2.06 (6H, d, J = 1.0 Hz), 1.30 (6H, s), 1.17 (6H, s), 0.69 (6H, t, J = 6.9 Hz).
FD-MS m/z=918.3（M⁺）

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.500 g (0.745 mmol) of ligand B, 0.176 g (1.49 mmol) of α-methylstyrene and 0.744 g of cyclopentylmethyl ether. 0.920 ml (1.51 mmol) of a 1.64M n-butyllithium hexane solution was added dropwise over 10 minutes. After raising the temperature to 60 ° C., the mixture was stirred for 4 hours. After cooling in an ice / acetone bath, the system was depressurized for 5 min and returned to normal pressure with nitrogen. 0.236 g (0.736 mmol) of hafnium tetrachloride was added. The reaction was allowed to proceed for 17 hours at room temperature. The solvent was distilled off, and the resulting solid was washed with hexane, and then the soluble matter was extracted with 150 ml of toluene, and the insoluble matter was removed by filtration. The resulting solution was concentrated and the precipitated solid was removed by filtration. The product was washed with toluene to obtain the target compound represented by the above formula [2B-2] (hereinafter referred to as “transition metal compound B”) as a powder. The yield was 0.520 g and the yield was 74%.
^The target product was identified from the measurement results of ¹ H-NMR and FD-MS. According to ¹ H-NMR, the powder contained 4.3 wt% toluene.
¹ H-NMR (THF-d8) δ: 7.81-7.74 (4H, m), 7.64 (2H, s), 7.19-7.11 (4H, m), 6.21 (2H, t, J = 2.7 Hz), 5.68 ( 2H, t, J = 2.7 Hz), 5.34 (2H, d, J = 1.3 Hz), 5.23 (2H, s), 2.93-2.70 (4H, m), 2.29 (6H, s), 2.06 (6H, d , J = 1.0 Hz), 1.30 (6H, s), 1.17 (6H, s), 0.69 (6H, t, J = 6.9 Hz).
FD-MS m / z = 918.3 (M ⁺ )

[Example 2C]
Synthesis of transition metal compound C (1) Synthesis of 6,6-di (4-fluorophenyl) fulvene 1.75 g of cyclopentadienyl lithium (purity 96.5 wt%, 23.4 mmol) in a 50 ml three-necked flask under nitrogen atmosphere 20 ml of cyclopentadienylmethyllithium was charged. Under an ice bath, 5.00 g (22.9 mmol) of 4,4′-difluorobenzophenone was added, and the mixture was stirred at room temperature for 20 hours and at 80 ° C. for 25 hours. 2.7 ml of dimethylimidazolidinone was added and stirred for 3.5 hours, and 2.02 g (purity 96.5 wt%, 27.1 mmol) of clopentadienyl lithium was further added and stirred for 15 hours. The reaction solution was poured into 120 ml of 0.5N hydrochloric acid. The organic layer was separated, the aqueous layer was extracted with 250 ml of hexane, and combined with the previous organic layer, washed with a saturated aqueous sodium bicarbonate solution, water, and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Purification by column chromatography (silica gel 200 g, hexane) and crystallization in an ethanol solvent gave 6,6-di (4-fluorophenyl) fulvene. The yield was 1.57 g and the yield was 26%.
¹ H-NMR (CDCl ₃ ) δ: 7.30-7.23 (4H, m), 7.10-7.02 (4H, m), 6.61-6.57 (2H, m), 6.24-6.20 (2H, m).
(2) Synthesis of ligand C

窒素雰囲気下、30mlシュレンク管にtert-ブチルメチルエーテル20ml、フルオレン化合物C 0.568g（1.38mmol）を装入した。この溶液にn-ブチルリチウムのヘキサン溶液（1.60M、0.90ml、1.4mmol）を氷水浴下、10分かけて滴下した。室温で18時間撹拌した。(1)で合成した6,6-ジ（4-フルオロフェニル）フルベン0.373g(1.43mmol)を加え、室温で4時間撹拌した。反応溶液に水100ml及びトルエン150mlを装入し、有機層を分離し、水、飽和塩化ナトリウム水溶液で洗浄した。硫酸マグネシウムで乾燥後、溶媒を留去し、メタノール洗浄することにより上記式[2C-1]で表される化合物（以下「配位子C」という。）を粉末として得た。収量0.819g、収率88％であった。
FD-MSの測定結果により、目的物を同定した。
FD-MS:m/Z=678.4(M⁺)

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 20 ml of tert-butyl methyl ether and 0.568 g (1.38 mmol) of fluorene compound C. To this solution, a hexane solution of n-butyllithium (1.60 M, 0.90 ml, 1.4 mmol) was added dropwise over 10 minutes in an ice-water bath. Stir at room temperature for 18 hours. 0.373 g (1.43 mmol) of 6,6-di (4-fluorophenyl) fulvene synthesized in (1) was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was charged with 100 ml of water and 150 ml of toluene, and the organic layer was separated and washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off, followed by washing with methanol to obtain a compound represented by the above formula [2C-1] (hereinafter referred to as “ligand C”) as a powder. The yield was 0.819 g and the yield was 88%.
The target product was identified from the FD-MS measurement results.
FD-MS: m / Z = 678.4 (M ⁺ )

  (3) Synthesis of transition metal compound C

窒素雰囲気下、30mlシュレンク管に配位子C 0.250g（0.354mmol）、α-メチルスチレン0.844g(0.714mmol)、シクロペンチルメチルエーテル0.353gを装入した。1.60Mのn-ブチルリチウムヘキサン溶液0.45ml（0.72mmol）を10分間で滴下した。40℃に昇温後、4時間撹拌した。氷/アセトン浴で冷却後、系内を5min減圧し、窒素で常圧に戻した。四塩化ハフニウム0.112g(0.351mmol)を加えた。室温で18時間反応させた。溶媒を留去し、得られた固体にトルエン40mlを加え、不溶物を濾過によって取り除いた。得られた溶液を濃縮し、析出した固体を濾過によって取り出した。トルエンで洗浄し、上記式[2C-2]で表される目的物（以下「遷移金属化合物C」という。）を粉末として得た。収量0.190g、収率59％であった。
¹H-NMR、FD-MSの測定結果により、目的物を同定した。
¹H-NMR (Toluene-d₈) δ: 7.79 (2H, s), 7.54-7.49 (2H, m), 7.47-7.40 (2H, m), 6.85-6.74 (4H, m), 6.22 (2H, t, J = 2.6 Hz), 5.68 (2H, t, J = 2.6 Hz), 5.19 (2H, s), 5.13 (2H, d, J = 1.0 Hz), 2.75-2.57 (4H, m), 1.95 (6H, d, J = 1.3 Hz), 1.10 (12H, s), 0.72 (6H, t, J = 6.9 Hz).
FD-MS m/z=926.2（M⁺）

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.250 g (0.354 mmol) of ligand C, 0.844 g (0.714 mmol) of α-methylstyrene and 0.353 g of cyclopentylmethyl ether. 0.45 ml (0.72 mmol) of a 1.60M n-butyllithium hexane solution was added dropwise over 10 minutes. After heating to 40 ° C., the mixture was stirred for 4 hours. After cooling in an ice / acetone bath, the system was depressurized for 5 min and returned to normal pressure with nitrogen. 0.112 g (0.351 mmol) of hafnium tetrachloride was added. The reaction was allowed to proceed for 18 hours at room temperature. The solvent was distilled off, 40 ml of toluene was added to the obtained solid, and insoluble matters were removed by filtration. The resulting solution was concentrated and the precipitated solid was removed by filtration. The product was washed with toluene to obtain the target compound represented by the above formula [2C-2] (hereinafter referred to as “transition metal compound C”) as a powder. The yield was 0.190 g and the yield was 59%.
^The target product was identified from the measurement results of ¹ H-NMR and FD-MS.
¹ H-NMR (Toluene-d ₈ ) δ: 7.79 (2H, s), 7.54-7.49 (2H, m), 7.47-7.40 (2H, m), 6.85-6.74 (4H, m), 6.22 (2H, t, J = 2.6 Hz), 5.68 (2H, t, J = 2.6 Hz), 5.19 (2H, s), 5.13 (2H, d, J = 1.0 Hz), 2.75-2.57 (4H, m), 1.95 ( 6H, d, J = 1.3 Hz), 1.10 (12H, s), 0.72 (6H, t, J = 6.9 Hz).
FD-MS m / z = 926.2 (M ⁺ )

[Comparative Example 2A]
Synthesis of transition metal compound d Referring to JP-A-2004-168774, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride (hereinafter referred to as "transition metal compound d") ") Was synthesized.

[Example 3A]
A gas-flowing glass polymerizer with an internal volume of 500 ml that has been thoroughly purged with nitrogen is charged with 250 ml of n-decane and 1.00 ml of 5-ethylidene-2-norbornene (ENB), and the temperature of the solution is adjusted to 100 ° C. And propylene were passed at normal pressure at 110 liter / hour and 40 liter / hour, respectively, to fully saturate the system. Then, a toluene solution of triisobutylaluminum (1.00 mol / l, 0.20 ml) was added. Toluene solution of transition metal compound A (2mmol / l, 3.00ml) and toluene solution of triphenylcarbenium tetrakis (pentafluoro) borate (5mmol / l, 2.40ml) were added and the system temperature was maintained. Polymerization was performed. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the supply of the ethylene / propylene mixed gas. The polymerization solution was placed in 1.5 L of a mixed solvent of methanol and acetone (volume ratio 7: 8) to which 1 ml of concentrated hydrochloric acid was added, and the mixture was sufficiently stirred and filtered. The polymer separated by filtration was washed with a large amount of methanol and then dried at 120 ° C. for 10 hours under reduced pressure. The evaluation results of the polymer are shown in Table 1.

[Examples 2B, 2C, Comparative Example 3A]
A polymer was obtained in the same manner as in Example 3A, except that the transition metal compound A was changed to the transition metal compound B, transition metal compound C, or transition metal compound d, respectively. The evaluation results of the obtained polymer are shown in Table 1.

  According to the present invention, since a high molecular weight olefin polymer can be produced efficiently, the fluorene compound, transition metal compound, olefin polymerization catalyst and production method of the present invention are extremely valuable industrially. Further, when a polyene is used in combination, an olefin polymer having a high polyene content can be efficiently produced with a high polyene monomer conversion, so that the production method of the present invention is extremely valuable industrially.

Claims (9)

A fluorene compound represented by the following general formula [I]:

(Where 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 , R ¹⁵ and R ¹⁶ is selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing hydrocarbon group, and may be the same or different.
Adjacent substituents from R ¹ to R ¹⁶ may be bonded to each other to form a ring. ) A fluorene compound represented by the following general formula [I ′]:

(Wherein R ⁰ is a metal-containing group, 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 , R ¹⁵ and R ¹⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing hydrocarbon group, and may be the same or different.
R ⁰ and R ² may be bonded to each other to form a ring, and adjacent substituents from R ² to R ¹⁶ may be bonded to each other to form a ring. ) A transition metal compound represented by the following general formula [II]:

Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group and a heteroatom-containing hydrocarbon group, The adjacent substituents from R ¹⁷ to R ²² may be different from each other to form a ring.
M is a Group 4 transition metal atom, Y is a carbon atom, a silicon atom or a germanium atom, Q is a neutral coordination that can be coordinated by a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron pair The same or different combinations are selected from the children, and j is an integer of 1 to 4.
Z is a fluorenylidene group having a divalent free valence having a structure obtained by removing R ¹ and R ² in the general formula [I] from the fluorene compound according to claim 1. ) The transition metal compound according to claim 3, wherein, in the general formula [II], R ¹⁹ , R ²⁰ , R ²¹ and R ²² are hydrogen atoms. The transition metal compound according to claim 3 or 4, wherein, in the general formula [I], R ³ , R ⁹ , R ¹⁰ and R ¹⁶ are hydrogen atoms.   The catalyst for olefin polymerization containing the transition metal compound of any one of Claims 3-5. (B-1) organometallic compounds,
It further contains (B-2) an organoaluminum oxy compound and (B-3) at least one compound (B) selected from compounds that react with the transition metal compound according to claim 3 to form an ion pair. The olefin polymerization catalyst according to claim 6.   And polymerizing at least one olefin selected from ethylene and an α-olefin having 3 to 30 carbon atoms in the presence of the olefin polymerization catalyst according to claim 6 or 7, Is a method for producing an olefin polymer, wherein ethylene is propylene.   The method for producing an olefin polymer according to claim 8, wherein the step of polymerizing the olefin in the presence of polyene is carried out.