JP2015199919A - Catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization which has excellent catalytic activity and provides a more useful olefin polymer, and to provide a method for producing the olefin polymer.SOLUTION: Provided is a catalyst for olefin polymerization comprising: as a post-metallocene compound, a transition compound component comprising a hafnium compound having a ligand where a pyridyl group and an amide group are bonded at the 2-position of the pyridyl group; and, further, at least one compound selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and a compound which reacts with a transition metal compound (I) to form an ion pair.

Description

  The present invention relates to an olefin polymerization catalyst containing a specific transition metal compound, and a method for producing an olefin polymer using the catalyst.

[Post metallocene compounds]
In recent years, post-metallocene compounds are well known as homogeneous catalysts for olefin polymerization (for example, Coord. Chem. Rev. 256 (2012) 2994-3007: Non-Patent Document 1).

  In the polymerization of olefins (including oligomerization) using post metallocene compounds, depending on the type of central metal and the structure and number of ligands of the post metallocene compound, the stereoregularity of the resulting olefin polymer, It is known that the molecular weight, comonomer composition, degree of branching, etc. vary greatly.

[Pyridyl-amide type transition metal compound]
Post metallocene compounds having a bidentate ligand containing a pyridyl group and an amide group are known to be useful olefin polymerization catalysts. For example, International Publication No. 99/01460 (Patent Document 1) discloses a transition metal compound having a ligand in which a pyridyl group and an amide group are bonded by a methylene chain.

  According to International Publication No. 2005/95469 (Patent Document 2), a post metallocene compound having a tridentate ligand bonded to a central metal via an oxygen atom in addition to a pyridyl group and an amide group is disclosed.

  Organometallics 2011, 30, 4854-4861 (Non-Patent Document 2) discloses a hafnocene compound having a ligand in which a pyridyl group and an amide group are bonded at the 2-position of the pyridyl group.

International Publication No. 2010/11435 (Patent Document 3) discloses a postmetallocene compound comprising a tridentate ligand having two pyridyl groups and one amide group.
In WO 2004/99268 (Patent Document 4), a tridentate ([CNN]) configuration in which a ligand in which a pyridyl group and an amide group are bonded by a methylene chain is further bonded to a central metal via a carbon atom. Post metallocene compounds having ligands are disclosed. In this post metallocene compound, it is reported that an olefin is inserted into a carbon-metal bond and an active species is generated in the presence of an olefin (J. AM. CHEM. SOC. 2007, 129, 7831-7840: non-patent) Reference 3). Further, it has been reported that such a compound gives a high molecular weight polymer as an olefin polymerization catalyst to a conventional metallocene compound, but is inferior in polymerization activity (Organometallics 2011, 30, 3318-3329: non-patent document). Reference 4). In addition, it has been reported that a compound having a similar structure also acts as a hydroamination catalyst (ChemCatChem, 2013, 5, 1142-1115: Non-Patent Document 5).

  Furthermore, it has been reported that a complex having a pyridyl-amide type [CNN] ligand having a similar structure functions as a multi-site catalyst (Dalton Trans., 2007, 42, 1501-1511: Non-Patent Document 6). ).

These post metallocene compounds are useful catalysts, and are particularly useful as olefin polymerization catalysts, but further improvements are required in polymerization activity and the like.
In general, since the polymerization reaction of olefin is an exothermic reaction, the cost for heat removal increases when polyolefin is produced at a low polymerization temperature. Therefore, if there are no other special restrictions, it is preferable from an economical viewpoint to manufacture at a higher polymerization temperature. Therefore, it can be said that a catalyst exhibiting higher polymerization activity at a higher polymerization temperature is more preferable.

[Coordinative Chain Transfer Polymerization]
The single-site catalyst typified by the post metallocene compound makes it possible to precisely control the structure of the polyolefin. Some of these catalysts are capable of living polymerization, and more versatile and precise structure control is possible. However, in living polymerization, one molecule of catalyst is required to produce one molecule of polymer. In general, the catalyst is expensive, and it has been difficult to utilize the living polymerization of polyolefin industrially.

In order to solve these problems, Coordinative Chain Transfer Polymerization has been actively studied (for example, Chem. Rev. 2013, 113, 3836-3857, Angew. Chem. Int. Ed. 2009, 2464: Non-patent document: 7). This polymerization mode has the following useful characteristics.
By using a chain transfer agent that is less expensive than the catalyst, a polymer of a plurality of molecules can be generated from a single molecule of the catalyst, which is economically advantageous over living polymerization.
The molecular weight of the polymer obtained depends on the ratio of the amount of polymer produced and the amount of chain transfer agent used. Therefore, the molecular weight can be controlled easily and over a wide range depending on the amount of the chain transfer agent used.
It is possible to produce a polymer having a highly reactive substituent derived from a chain transfer agent at the terminal. For example, if Coordinative Chain Transfer Polymerization can be performed using an organoaluminum compound as a chain transfer agent, a polymer having an Al-containing group at a terminal can be obtained, and different substituents can be introduced by various reactions (for example, Macromol. Symp., 2004, 213, 335-345: Non-Patent Document 8).

  As a specific example of Coordinative Chain Transfer Polymerization, Organometallics, 2011, 30, 4854-4861 (Non-patent Document 9), hafnocene having a ligand in which a pyridyl group and an amide group are bonded at the 2-position of the pyridyl group. Although examples of polymerization using compounds are disclosed, it is difficult to say that polymerization activity and chain transfer efficiency are sufficient.

  Science, 2006, 312, 714 (Non-Patent Document 10), Chain Shutting Polymerizations technology using a hafnium compound having a ligand in which a pyridyl group and an amide group are bonded by a methylene chain, and a zinc compound as a chain transfer agent. Is disclosed.

  However, in this technique, an expensive zinc compound is substantially essential as a chain transfer agent, so it is difficult to say that the technique is economically sufficient. In these catalysts, the polymerization activity may be reduced depending on the amount of the chain transfer agent.

  In order to solve such problems, International Publication No. 2011/156742 (Patent Document 5) discloses a technique in which a zinc compound and an inexpensive aluminum compound are used in combination as a chain transfer agent. It is difficult to say that the polymerization activity is sufficient.

Chem. Eur. J. et al. , 2006, 12, 8969 (Non-patent Document 11) discloses an example of Chain Transfer Polymerization using organoaluminum as a chain transfer agent using an yttrium compound having a pyridyl-amide type [NN] ligand. The polymerization activity was very low, and the tendency was remarkable especially at high temperatures.
From the above situation, there has been a demand for a highly active catalyst that enables Chain Transfer Polymerization using an inexpensive chain transfer agent.

International Publication No. 99/01460 International Publication No. 2005/95469 International Publication No. 2010/11435 International Publication No. 2004/99268 International Publication No. 2011/156742

Coord. Chem. Rev. 256 (2012) 29994-3007 Organometallics 2011, 30, 4854-4861 J. et al. AM. CHEM. SOC. 2007, 129, 7831-7840 Organometallics 2011, 30, 3318-3329 ChemCatChem, 2013, 5, 1142-1151 Dalton Trans. , 2007, 42, 1501-1511 Chem. Rev. 2013, 113, 3836-3857, Angew. Chem. Int. Ed. 2009, 2464 Macromol. Symp. , 2004, 213, 335-345 Organometallics, 2011, 30, 4854-4861 Science, 2006, 312, 714 Chem. Eur. J. et al. , 2006, 12, 8969

  An object of the present invention is to provide an olefin polymerization catalyst having excellent catalytic activity and providing a useful olefin polymer, and a method for producing the olefin polymer.

  The present inventors have 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.

  That is, the catalyst for olefin polymerization according to the present invention is characterized by containing a transition metal compound (I) represented by the following general formula (I).

(In the general formula (I), Q ^{1 to} Q ⁵ each independently represents a carbon atom or a silicon atom, and a single bond between adjacent atoms of Q ^{1 to} Q ⁵ is replaced by a multiple bond. R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, or a phosphorus-containing group. , A silicon-containing group, a germanium-containing group, or a tin-containing group, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, sulfur May be substituted by at least one substituent selected from a containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and two or more of these R ^{1 to} R ¹⁰ are connected to each other. Forming a ring The hydrogen atom contained in the ring may be a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group. When at least one substituent selected from a group, a germanium-containing group, and a tin-containing group may be substituted, and a single bond between adjacent atoms among Q ^{1 to} Q ⁵ is replaced with a multiple bond Is a part of R ^{1 to} R ¹⁰ depending on the valence of the multiple bond, T represents a nitrogen atom or a phosphorus atom, A represents a hydrocarbon group or a hetero element-containing hydrocarbon group. , X represents a C1-C30 cyclic hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, M represents a group 3-10 transition metal element in the periodic table, and X and M Dotted line between and indicates coordination bond , L represents a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated by a lone pair, n is an integer of 1 to 4, and when n is 2 or more, L May be the same or different.)
As the transition metal compound (I), the moiety represented by Q ³ (R ⁵ R ⁶ ) —XQ ⁴ (R ⁷ R ⁸ ) in the above general formula (I) is a structure of the following general formula (II) The compound shown by these is preferable.

(In the general formula (II), R ^{11 to} R ¹³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{11 to} R ¹³ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and Q ³ , Q ⁴ and R ^{5 to} R ⁸ is the same as defined in general formula (I).)
Transition metal compound as the (I), in the above general formula (I), ^{X-Q 4 (R 7 R} 8) -Q 5 (R 9 R 10) moieties represented by -M, following general formula (III) A compound represented by the structure:

(In the general formula (III), R ^{14 to} R ¹⁷ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{14 to} R ¹⁷ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and X and M in the general formula (I) Same as definition.)
The transition metal compound (I), in the above general formula (I), ^{X-Q 3 (R 5 R} 6) -Q 2 (R 3 R 4) moieties represented by -Q ¹ (R ¹ R ²⁾ A compound represented by the structure of the following general formula (IV) is preferable.

(In the general formula (IV), R ^{18 to} R ²¹ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{18 to} R ²¹ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and X, Q ¹ , R ¹ and R ² Is the same as defined in general formula (I).)
As the transition metal compound (I), a compound in which the moiety represented by TA in the general formula (I) is represented by the structure of the following formula (VII) is preferable.

(In the formula (VII), R ²⁶ ~R ³⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, shows a hetero element-containing hydrocarbon group having 1 to 30 carbon atoms, these R ²⁶ ~ Two or more of R ³⁰ may be connected to each other to form a ring, and the hydrogen atom contained in the ring is further a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group And may be substituted with at least one substituent selected from a group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

In the general formula (VII), it is preferable that at least one selected from R ²⁶ and R ³⁰ is a hydrocarbon group having 1 to 30 carbon atoms.
A compound in which T is a nitrogen atom and A is an aryl group, T is a nitrogen atom, and hydrocarbon having 1 to 30 carbon atoms in the ortho position when A is based on an atom bonded to T More preferred are compounds that are aryl groups having one or two groups.

As the transition metal compound (I), in the general formula (I), a compound in which M is a Group 4 transition metal element in the periodic table is preferable, and a compound in which M is hafnium is more preferable.
The catalyst for olefin polymerization according to the present invention, in addition to the transition metal compound (I),
(B-1) an organometallic compound,
Preferably, it contains at least one compound (B) selected from (B-2) an organoaluminum oxy compound and (B-3) a compound that forms an ion pair by reacting with the transition metal compound (I). It is an aspect.

In addition to the transition metal compound (I) and the (B-1) organometallic compound, the olefin polymerization catalyst according to the present invention further includes:
It is also preferable to contain at least one compound selected from the above (B-2) organoaluminum oxy compound and (B-3) a compound that reacts with the transition metal compound (I) to form an ion pair. It is an aspect.

  The method for producing an olefin polymer according to the present invention comprises 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. .

  The catalyst for olefin polymerization of the present invention is excellent in catalytic activity and provides a useful olefin polymer.

FIG. 1 is a model diagram of the three-dimensional structure of the transition metal compound A obtained in Example 1A. FIG. 2 is a model diagram of the three-dimensional structure of the transition metal compound B obtained in Example 1B. FIG. 3 is a model diagram of the three-dimensional structure of the transition metal compound C obtained in Example 1C. FIG. 4 is a model diagram of the three-dimensional structure of the transition metal compound D obtained in Example 1D. FIG. 5 is a model diagram of the three-dimensional structure of the transition metal compound E obtained in Example 1E. FIG. 6 is a model diagram of the three-dimensional structure of the transition metal compound F obtained in Example 1F. FIG. 7 is a model diagram of the three-dimensional structure of the transition metal compound G obtained in Example 1G. FIG. 8 is a model diagram of the three-dimensional structure of the transition metal compound H obtained in Example 1H. FIG. 9 is a model diagram of the three-dimensional structure of the transition metal compound b obtained in Synthesis Example 1b. FIG. 10 shows the results of ¹³ C-NMR measurement of ethylene / propylene block copolymer (Example 7A). FIG. 11 is a temperature rising elution fractionation curve (TREF curve) obtained from cross fraction chromatography (CFC) measurement of ethylene / propylene block copolymer (Example 7A).

  Hereinafter, the transition metal compound (I) represented by the general formula (I) used in the production method of the present invention, the production method of the transition metal compound (I), and the olefin polymerization catalyst containing the transition metal compound (I) A description will be made sequentially.

  In the present specification, a compound represented by the formula (X) (X is a formula number) is also referred to as “compound (X)”, and a structural unit derived from the compound A in the description of the polymer is referred to as “compound A unit”. The content thereof is also referred to as “compound A content”.

[Transition metal compound (I)]
The transition metal compound (I) is represented by the following general formula (I).

In the general formula (I), Q ^{1 to} Q ⁵ each independently represent a carbon atom or a silicon atom, and a single bond between adjacent atoms of Q ^{1 to} Q ⁵ may be replaced with a multiple bond. Well, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, A silicon-containing group, a germanium-containing group, or a tin-containing group, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, or a sulfur-containing group. May be substituted with at least one substituent selected from a group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and two or more of these R ^{1 to} R ¹⁰ may be linked to each other to form a ring Forming The hydrogen atom contained in the ring may be a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group. , A germanium-containing group, and a tin-containing group may be substituted with at least one substituent, and when a single bond between adjacent atoms of Q ^{1 to} Q ⁵ is replaced with a multiple bond , Part of R ^{1 to} R ¹⁰ will not be present depending on the valence of the multiple bond, T represents a nitrogen atom or a phosphorus atom, A represents a hydrocarbon group or a hetero element-containing hydrocarbon group, X represents a C1-C30 cyclic hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, M represents a group 3-10 transition metal element in the periodic table, and X and M The dotted line between indicates a coordination bond L represents a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand that can be coordinated by a lone electron pair, n is an integer of 1 to 4, and when n is 2 or more, L is It may be the same or different.

  "Hetero" or "heteroelement" represents an element that is not a carbon atom or a hydrogen atom, and particularly represents a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a silicon atom, a boron atom, a germanium atom, or a tin atom. A “heterocyclic compound” is a cyclic compound containing these hetero elements as elements constituting a ring. The hetero element-containing hydrocarbon group is a group containing a hetero element, carbon, and hydrogen. For example, a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus -Containing group, silicon-containing group, germanium-containing group, tin-containing group, and hydrogen atom contained in hydrocarbon group are halogen atoms, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur And a group substituted with at least one substituent selected from a containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

<Q ¹ to Q ⁵ and R ¹ to R ^10>
Examples of the halogen atom that can be R ^{1 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group that can be R ^{1 to} R ¹⁰ include 1 or 2 of a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, or a saturated hydrocarbon group. A group formed by substituting the above hydrogen atom with a cyclic unsaturated hydrocarbon group is exemplified. Carbon number of a hydrocarbon group is 1-30 normally, Preferably it is 1-20, More preferably, it is 1-10.

  Examples of the linear hydrocarbon group include 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. And linear alkyl groups such as n-decanyl group; linear alkenyl groups such as 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, and 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a methylcyclohexyl group; a polycyclic saturated hydrocarbon such as a norbornyl group, an adamantyl group, and a methyladamantyl group Group and the like.

  Examples of the cyclic unsaturated hydrocarbon group include aryl groups such as phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group and fluorenyl group; cycloalkenyl group such as cyclohexenyl group; 5-bicyclo [2. 2.1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group. Further, at least one hydrogen atom contained in these cyclic unsaturated hydrocarbon groups has the above-mentioned linear hydrocarbon group, branched hydrocarbon group, cyclic saturated hydrocarbon group, or saturated hydrocarbon group described later. One or two or more hydrogen atoms may be substituted with a group obtained by substituting a cyclic unsaturated hydrocarbon group.

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

  Further, the hydrogen atom contained in these hydrocarbon groups includes the halogen atom described above, the heterocyclic compound residue described later, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group. , A germanium-containing group, and a tin-containing group may be substituted with at least one substituent.

Examples of the heterocyclic compound that is the base of the heterocyclic compound residue that can be R ^{1 to} R ¹⁰ include furan, tetrahydrofuran, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, and furazane. , Pyran, pyridine, pyridazine, pyrimidine, pyrazine, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, indole, isoindole, indazole, chromene, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, quinazine , Purine, pteridine, xanthene, carbazole, phenanthridine, acridine, phenazine, phenanthroline, indoline, isoindoline, chroma And, different isomers of the double bond position in these, or hetero atom position included in thereof are different isomers. Further, the hydrogen atoms contained in these heterocyclic compounds are the halogen atom, hydrocarbon group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group described later, It may be substituted with at least one substituent selected from a germanium-containing group and a tin-containing group.

Examples of the oxygen-containing group that can be R ^{1 to} R ¹⁰ include, in addition to the above-described heterocyclic compound residue, for example, an alkoxy group such as a methoxy group, an ethoxy group, and tert-butyloxy, an aryloxy group such as a phenoxy group, and a quinolinol group. And aryloxy groups containing other hetero elements such as carbonyl groups such as acetyl groups. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , or R ⁹ and R ¹⁰ are connected to each other to form a ring, for example, a ring containing an acetal structure It may be.

Examples of the nitrogen-containing group that can be R ^{1 to} R ¹⁰ include amino groups such as N-methylamino group, N, N-dimethylamino group, and N-phenylamino group, in addition to the above-described heterocyclic compound residues. Examples include amide groups such as acetylamino group, imide groups such as succinimide group, cyano groups, and nitro groups.

Examples of the boron-containing group that can be R ^{1 to} R ¹⁰ include dimethylboryl group, dicyclohexylboryl group, 9-borabicyclohexyl [3.3.1] nonane-9-yl group, triphenylboryl group, and dimethoxyboryl group. And groups having a boron atom and an oxygen atom such as a boryl group and a catecholboryl group.

Examples of the sulfur-containing group that can be R ^{1 to} R ¹⁰ include substituents having an oxygen atom such as a phenylsulfinyl group and a phenylsulfonyl group in addition to the above-described heterocyclic compound residue, for example, a methylthio group and a phenylthio group. Etc. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , or R ⁹ and R ¹⁰ are connected to each other to form a ring, for example, a ring containing a thioacetal structure It may be.

Examples of the phosphorus-containing group that can be R ^{1 to} R ¹⁰ include a dimethylphosphino group, a ditert-butylphosphino group, a dicyclohexylphosphino group, a diphenylphosphino group, a dimethoxyphosphino group, and a dimethylphosphine oxide group. And a group having a phosphorus atom and an oxygen atom.

Examples of the silicon-containing group that can be R ^{1 to} R ¹⁰ include a trimethylsilyl group, a hydrodimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group.

Examples of the germanium-containing group that can be R ^{1 to} R ¹⁰ include a trimethylgermyl group, a hydrodimethylgermyl group, a tert-butyldimethylgermyl group, and a triphenylgermyl group.

Examples of tin-containing groups that can be R ^{1 to} R ¹⁰ include a trimethylstannyl group, a hydrodimethylstannyl group, a tert-butyldimethylstannyl group, and a triphenylstannyl group.

Although there is no restriction | limiting in particular in the number of the carbon atoms contained in the above-mentioned substituent, Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-10.
Among the above R ^{1 to} R ¹⁰ , a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group and a nitrogen-containing group are preferable, a hydrogen atom and a hydrocarbon group are more preferable, a hydrogen atom and a heteroelement A hydrocarbon group containing no is more preferable.

Q ^{1 to} Q ³ are each independently a carbon atom or a silicon atom, and more preferably a carbon atom. A single bond between adjacent atoms among Q ^{1 to} Q ³ may be replaced with a multiple bond.

Above formula (I), from Q ¹ to Q ³ and R ¹ including ^{R 6, X-Q 3 (} R 5 R 6) -Q 2 (R 3 R 4) -Q 1 (R 1 R 2) It is preferable that the part shown by is a structure shown by the structure of the following general formula (IV).

In the general formula (IV), R ^{18 to} R ²¹ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of R ^{18 to} R ²¹ may be linked to each other to form a ring, and the ring is further a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, boron It may have at least one substituent selected from a containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Among these R ^{18 to} R ²¹ , preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, more preferably a carbon atom containing no hydrogen atom or heteroelement. ˜20 hydrocarbon groups. Among the structures represented by the above formula (IV), a structure in which R ¹ and R ² are hydrogen atoms and R ¹⁸ to R ²⁵ are hydrogen atoms is particularly preferable. In the general formula (IV), X, Q ¹ , R ¹ and R ² are the same as defined in the general formula (I).

Among the general formula (IV), a structure represented by the following general formula (V) is particularly preferable. In general formula (V), the definitions and preferred embodiments of R ^{18 to} R ²¹ , X, R ¹ and R ² are the same as in general formula (IV).

In the above formula (I), from Q ¹ to Q ³ and R ¹ including ^{R 6, X-Q 3 (} R 5 R 6) -Q 2 (R 3 R 4) -Q 1 (R 1 R ^The portion represented by ² ) is also preferably a structure represented by the structure of the following general formula (IV ′).

In the general formula (IV ′), R ^{22 to} R ²⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{22 to} R ²⁵ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Among these R ^{22 to} R ²⁵ , preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, more preferably a carbon atom containing no hydrogen atom or heteroelement. ˜20 hydrocarbon groups. Among the structures represented by the above formula (IV ′), a structure in which R ⁵ and R ⁶ are hydrogen atoms and R ²² to R ²⁵ are hydrogen atoms is particularly preferable. In the general formula (IV ′), X, Q ³ , R ⁵ and R ⁶ are the same as defined in the general formula (I).

Among the general formula (IV ′), a structure represented by the following general formula (VI) is particularly preferable. In general formula (VI), the definitions and preferred embodiments of R ^{22 to} R ²⁵ , X, R ⁵ and R ⁶ are the same as those in general formula (IV).

Q ⁴ and Q ⁵ are each independently a carbon atom or a silicon atom, more preferably a carbon atom. A single bond connecting Q ⁴ and Q ⁵ may be replaced with a multiple bond.

In the general formula (I), Q ⁴ , Q ⁵ include R ⁷ to R ^10, and the moiety represented by X-Q ⁴ (R ⁷ R ⁸ ) -Q ⁵ (R ⁹ R ¹⁰ ) -M is A structure represented by the structure of the following general formula (III) is preferable.

In the general formula (III), R ^{14 to} R ¹⁷ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of R ^{14 to} R ¹⁷ may be connected to each other to form a ring, and the ring is further a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, boron It may have at least one substituent selected from a containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Among these R ^{14 to} R ¹⁷ , preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, more preferably a carbon atom containing no hydrogen atom or heteroelement. ˜20 hydrocarbon groups.
In the general formula (III), X and M are the same as defined in the general formula (I).

<X>
X is a C1-C30 cyclic hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, preferably the number of carbon atoms containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom 1 to 20 cyclic hydrocarbon groups, more preferably two hydrogen atoms are removed from a cyclic hydrocarbon compound having a hetero element having an atom selected from a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom. It is a divalent residue (hereinafter also referred to as a cyclic hydrocarbon compound residue having a hetero element). Examples of the cyclic compound that is the basis of the cyclic hydrocarbon compound residue having a hetero element include furan, tetrahydrofuran, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, pyran, Pyridine, pyridazine, pyrimidine, pyrazine, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, indole, isoindole, indazole, chromene, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine Pteridine, xanthene, carbazole, phenanthridine, acridine, phenazine, phenanthroline, indoline, isoindoline, chroman, Beauty, different isomers of the double bond position in these, or hetero atom position and the like are different isomers contained in these. Further, the hydrogen atoms contained in these heterocyclic compounds are the halogen atom, hydrocarbon group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group described later, It may be substituted with at least one substituent selected from a germanium-containing group and a tin-containing group.

Among the above X, divalent residues based on furan, thiophene, pyrrole, or pyridine ring are more preferable.
The cyclic hydrocarbon compound residue having a hetero element that can be X is coordinated to M via a hetero element contained in X. Q ³ and Q ⁴ are bonded to atoms adjacent to the hetero element. Bonding is preferred.

As one of the most preferable embodiments of the partial structure containing X, a moiety represented by Q ³ (R ⁵ R ⁶ ) —XQ ⁴ (R ⁷ R ⁸ ) in the general formula (I) is represented by the following general formula: The structure shown by the structure of (II) is mention | raise | lifted.

In the general formula (II), R ^{11 to} R ¹³ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of R ^{11 to} R ¹³ may be connected to each other to form a ring, and the ring is further a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, boron It may have at least one substituent selected from a containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Among these R ^{11 to} R ¹³ , preferably a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, or a nitrogen-containing group, more preferably carbon that does not contain a hydrogen atom or a hetero element. It is a hydrocarbon group of 1 to 20 and more preferably a hydrogen atom.
In the general formula (II), Q ³ , Q ⁴ and R ^{5 to} R ⁸ are the same as defined in the general formula (I).

<T, A>
T is a nitrogen atom or a phosphorus atom, preferably a nitrogen atom.
A is a hydrocarbon group or a heteroelement-containing hydrocarbon group, preferably a hydrocarbon group having 1 to 30 carbon atoms or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, more preferably the number of carbon atoms. It is a 1-20 hydrocarbon group or a C1-C20 hetero element containing hydrocarbon group. Examples of the hydrocarbon group that can be A include the groups described above as the hydrocarbon groups that can be R ^{1 to} R ¹⁰ . The hetero element-containing hydrocarbon group that can be A is a group containing a hetero element, carbon, and hydrogen as described above. The hetero-element-containing hydrocarbon group that can be A includes oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups exemplified as groups that can be R ^{1 to} R ^10. And tin-containing groups. In addition, as the heteroelement-containing hydrocarbon group that can be A, the hydrogen atom contained in the hydrocarbon group is a halogen atom, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, And a group substituted with at least one substituent selected from a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group.

Among the above A, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a heterocyclic compound residue are preferable. Examples of these groups include a cyclic saturated hydrocarbon group that can be R ^{1 to} R ^10, and a cyclic unsaturated hydrocarbon. The group illustrated as a hydrogen group and a heterocyclic compound residue is mentioned. The hydrogen atoms contained in these groups are halogen atoms, hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups. It may be substituted with at least one substituent selected from

A is preferably a group having a hydrocarbon group or a hetero element-containing hydrocarbon group at two atoms adjacent to an atom bonded to T, more preferably two atoms adjacent to an atom bonded to T; A cyclic unsaturated hydrocarbon group having a hydrocarbon group or a hetero element-containing hydrocarbon group.
As the moiety represented by T-A, a structure represented by the following formula (VII) is more preferable.

In the formula (VII), R ^{26 to} R ³⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hetero element-containing hydrocarbon group having 1 to 30 carbon atoms, and these R ^{26 to} R 30 Two or more of ³⁰ may be connected to each other to form a ring, and the hydrogen atom contained in the ring is further a halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group , A boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and may be substituted with at least one substituent.

Among these R ^{26 to} R ³⁰ , a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, and a nitrogen-containing group are preferable, and the carbon number of 1 to 20 not containing a hydrogen atom or a hetero element The hydrocarbon group is more preferable. Among the groups represented by the formula (VII), at least one of R ²⁶ and R ³⁰ is a hydrocarbon group having 1 to 20 carbon atoms, R ²⁷ and R ²⁹ are hydrogen atoms, and R ²⁸ is a hydrogen atom or carbon number. and it is preferably from 1 to 20 embodiment is a hydrocarbon group, R ²⁶ and R ³⁰ is a hydrocarbon group having 1 to 20 carbon atoms, R ²⁷ and R ²⁹ are hydrogen atoms, R ²⁸ is a hydrogen atom or a carbon atoms More preferably, it is an embodiment of 1 to 20 hydrocarbon groups.

  Particularly preferred embodiments of A include, for example, 2,6-diisopropylphenyl group, 2,6-dimethylphenyl group, 2,6-dicyclohexylphenyl group, 2,4,6-trimethylphenyl group, 2,6-diisopropyl- 4-methylphenyl group etc. are mentioned.

<M, L, n>
M represents a transition metal atom of Groups 3 to 10 of the Periodic Table (Group 3 includes lanthanoids), preferably a transition metal atom of Group 3 to 9 (Group 3 also includes lanthanoids), A transition metal atom selected from Group 3 to 6 is more preferable, a transition metal atom selected from Group 4 or 6 is more preferable, and a transition metal atom of Group 4 is particularly preferable. Here, the number of the element group follows a nomenclature represented by 1 to 18 numerals defined by IUPAC. Examples of transition metal atoms that can be M include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel, and palladium. And platinum. Among these M, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, iron and the like are preferable, and titanium, zirconium, hafnium, vanadium, chromium, iron, yttrium and the like are more preferable. Titanium, zirconium, and hafnium are more preferable, and hafnium is most preferable.

Examples of the halogen atom that can be L include fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group that can be L include the groups described above as the hydrocarbon groups that can be R ^{1 to} R ¹⁰ . Among these hydrocarbon groups, a group obtained by substituting one or more hydrogen atoms of an alkyl group such as a linear alkyl group or a branched alkyl group or a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group is preferable. , A methyl group and a benzyl group are more preferable, and a methyl group is particularly preferable.

  Examples of anionic ligands that can be L include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; dimethylamide and diisopropyl Amide groups such as amide, methylanilide, diphenylamide and the like can be mentioned.

  Examples of the neutral ligand that can be coordinated by a lone electron pair that can be L include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1, 2, -Ethers such as dimethoxyethane.

It is preferable that at least one of the L is a halogen atom or an alkyl group.
n is an integer of 1 to 4, preferably 2.
The preferred embodiments of the configuration of the transition metal compound (I), that is, R ^{1 to} R ³⁰ , X, T, A, M, L, and n have been described above. In the present invention, any combination of preferred embodiments is also a preferred embodiment, but a transition metal compound represented by the following general formula (VIII) is more preferred.

In the general formula (VIII), R ^{11 to} R ²¹ , R ^{26 to} R ³⁰ , M, L, and n are the same as defined in formula (I), formula (II), formula (V), and formula (VII). is there. Among the transition metal compounds represented by the general formula (VIII), a preferable embodiment is that R ¹ , R ² , R ^{11 to} R ²¹ , R ^{26 to} R ³⁰ and L are each independently a hydrogen atom or a halogen atom. , Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, or nitrogen-containing group, M is zirconium or hafnium, and n is 2, preferably a transition metal compound, R ¹ , R ² , R ^{11 to} R ²¹ and R ^{26 to} R ³⁰ are each independently a hydrocarbon group having 1 to 20 carbon atoms that does not contain a hydrogen atom or a hetero element, and L is 1 to 20 carbon atoms that does not contain a hydrogen atom or a hetero element. And a transition metal compound in which M is hafnium.

<Specific examples of transition metal compound (I)>
Preferred transition metal compounds (I) used in the present invention include, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6- Diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl)- 2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6- Diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ -N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N -(2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- ( 4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl) -Κ-C2) Lysine-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridine-2] -Yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5 '-Di-tert-butyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-diisopropylaniline-κ-N] dimethyl Hafnium is mentioned.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl ) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline -Κ-N] dimethylhafnium, [N- (2- (6 (4-tert-Butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4 -Adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl- κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2)] Pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridine-2- Yl-κ-N) benzyl) -2 6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethyl Aniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl- κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl) -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N ) Benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl)- 2,4,6-trimethylaniline-κ-N] dimethylhough [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethyl Hafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N -(2- (6- (4-Fluorophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- ( 2- (6- (4-Methylthiophenyl-κ- C2) Pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) ) Pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1] , 1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,4 6-trimethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl ) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline -Κ-N] dimethylhafnium, [N- (2- (6 (4-tert-Butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4 -Adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl- κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethyl hafnium, [N- (2- (6- (4-fluorophenyl-κ-C2)] Pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridine-2- Yl-κ-N) benzyl) -2 6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethyl Aniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl- κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl) -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridine-2 -Yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridine] -2-yl-κ-N) benzyl) -2,4,6-tri -Tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4 , 6-Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2 , 4,6-Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) Benzyl) -2,4,6-tri-te t-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6- Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4 , 6-Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ- C3) Pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5 ′) -Di-tert-butyl- [1,1'-biphenyl] -4-yl -Κ-C3) pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline -Κ-N] Ruhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium , [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (4-Fluorophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4 -Methyl Ophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ) -C2) Pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1 , 1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6 -(3 ', 5'-di-tert-butyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline -Κ-N] dimethylhafnium Is mentioned.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl ) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline -Κ-N] dimethylhafnium, [N- ( -(6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4 -Methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl- κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2)] Pyridin-2-yl-κ-N Benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) benzyl)- 2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridine] -2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1 , 1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2, 6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl)- 2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl)- 2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl)- 2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl)- 2,6-di Sopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2, 6-Diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3biphenyl] -4 -Yl-κ-C3) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′ , 5′-di-tert-butyl- [ , 1'-biphenyl] -4-yl-kappa-C3) pyridin-2-yl-kappa-N) -4-methylbenzyl) -2,6-diisopropylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenz ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxy Benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-) C3) Pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di) -Tert-butyl- [1,1'- Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenz ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluoro Benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-) C3) Pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di) -Tert-butyl- [1,1'- Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-dimethylanily -Κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium , [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methyl Benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4- Yl-κ-C3) pyridin-2-yl-κ-N) -4-methylbenzyl) -2 6-dimethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-dimethyl Ruaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Dimethylaniline-κ-N] di Tilhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N)- 4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) -4 Methoxybenzyl) -2,6-dimethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-dimethyl Ruaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Dimethylaniline-κ-N] di Tilhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N)- 4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) -4 Fluorobenzyl) -2,6-dimethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridine-2] -Yl-κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridine] -2-yl-κ-N) -4-methylbenzyl) -2, 4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N)- 4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) ) -4-Methylbenzyl) -2,4,6 Trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4, 6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2 , 4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) Pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di) -Tert-butyl- [1,1'-biphenyl] -4-yl -Κ-C3) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridine-2] -Yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridine] -2-yl-κ-N) -4-methoxybenzyl ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N)- 4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) ) -4-Methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl] -Κ-N) -4-Methoxybenz ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl]-) 4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′- Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridine-2]. -Yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridine] -2-yl-κ-N) -4-fluorobenzyl ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N)- 4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) ) -4-Fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl] -Κ-N) -4-fluorobenze ) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl]-) 4-yl-κ-C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′- Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-diethylanily -Κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium , [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methyl Benzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4- Yl-κ-C3) pyridin-2-yl-κ-N) -4-methylbenzyl) -2 6- diethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-diethi Ruaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6 -Diethylaniline-κ-N] di Tilhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N)- 4-methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) -4 Methoxybenzyl) -2,6-diethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-diethi Ruaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6 -Diethylaniline-κ-N] di Tilhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N)- 4-fluorobenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) -4 Fluorobenzyl) -2,6-diethylaniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl). -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridine- 2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-) [kappa] -C2) pyridin-2-yl- [kappa] -N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline- [kappa] -N] dimethylhafnium, [N- (2- (6- (4-Isopropylphenyl-κ-C2) pyridin-2-yl-κ -N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) ) Pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4- Adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Fluoro Phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [ N- (2- (6- (4-Dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ -N] dimethylhafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N ) -4-Methylbenzyl) -2,4,6-tri-tert- Tyraniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridine- 2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridine] -2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl) -Κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6 -(4-Isopropylphenyl-κ-C2) pyridine-2 Yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-) κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] Dimethyl hafnium, [N- (2- ( -(4-Fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N -(2- (6- (4-Methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N ] Dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert -Butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridine-2- Yl-κ-N) -4-methoxybenzyl) -2, , 6-Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4- Yl-κ-C3) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridine] -2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl) -Κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6 -(4-Isopropylphenyl-κ-C2) pyridine-2 Yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-) κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-Methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] Dimethyl hafnium, [N- (2- ( -(4-Fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N -(2- (6- (4-Methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N ] Dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert -Butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridine-2- Yl-κ-N) -4-fluorobenzyl) -2, , 6-Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4- Yl-κ-C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methyl Benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methyl Benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methyl Benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methyl Benzyl -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) ) Pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-) tert-Butyl- [1,1′- Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybe Ndyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4 − Toxibenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-) [kappa] -C3) pyridin-2-yl- [kappa] -N) -4-methoxybenzyl) -2,6-dicyclohexylaniline- [kappa] -N] dimethylhafnium, [N- (2- (6- (3 ', 5') -Di-tert -Butyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium Is mentioned.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobe Ndyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4 -Fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4 − Fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluoro Benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ) -C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′- J-tert -Butyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium Is mentioned.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl]. ) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methylbenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methylbenzyl) -2,6-dipheni Ruaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diphenylaniline-κ-N] di Tilhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diphenylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diphenylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3 ', 5'-dimethyl- [1,1'-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N)- 4-methylbenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl]) -4-yl-κ-C3) pyridin-2-yl-κ-N) -4 Include methylbenzyl) -2,6-diphenyl-aniline-kappa-N] dimethyl hafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl]. ) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-methoxybenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-methoxybenzyl) -2,6- Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2, 6-Diphenylani -Κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diphenyl Aniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6- Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -4-methoxybenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1 , 1′-biphenyl] -4-yl-κ-C3) pyridine- - yl-kappa-N)-4-methoxybenzyl) -2,6-diphenyl-aniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl]. ) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ] -N) -4-fluorobenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl) -2,6- Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2, 6-Diphenylani -Κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diphenyl Aniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6- Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -4-fluorobenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1 , 1′-biphenyl] -4-yl-κ-C3) pyridine- - yl-kappa-N)-4-fluorobenzyl) -2,6-diphenyl-aniline-kappa-N] dimethyl hafnium and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (phenyl (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) methyl]. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl) -Κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl) -Κ-N) Phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-) N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-) N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-) N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-fluorophenyl-κ-C2) pyridine)- 2-yl-κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-methylthiophenyl-κ-C2) pyridine)- 2-yl-κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (4-dimethylaminophenyl-κ-C2) pyridine) -2-yl-κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (3 ′, 5′-dimethyl- [1 , 1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (phenyl ( 2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) phenyl) methyl) -2, 6-Diisopropylaniline-κ-N] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (1- (2- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) phenyl). Ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl- κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ- N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) Phenyl) ethyl) -2,6-diiso Propylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6- Diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline -Κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ -N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ- ] Dimethyl hafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethyl Hafnium, [N- (2- (6- (4-Dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium , [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (1- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4 -Yl-κ-C3) pyridin-2-yl- -N) phenyl) ethyl) -2,6-diisopropylaniline-kappa-N] dimethyl hafnium and the like.

Moreover, as preferable transition metal compound (I) used by this invention, for example,
[N-((3- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalene- 2-yl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridine] 2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydro Naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhuff Ni, [N- (2- (6- (4-Isopropylphenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8- Octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl- κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- ( 2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalene-2- Yl) -2,6-diisopropylaniline-κ- Dimethyl hafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8, 8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl- κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- ( 2- (6- (4-Methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalene-2- Yl) -2,6-diisopropylaniline-κ N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5 8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1 ′) -Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalen-2-yl)- 2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-di-tert-butyl- [1,1′-biphenyl] -4-yl-κ) -C3) Pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5 , 8,8-Octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridine) 2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -5,5,8,8-octamethyl-5,5,8,8-octa Hydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ) -N) -5,5,8,8-octamethyl Ru-5,5,8,8-octahydronaphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium biphenyl] -4-yl-κ-C3 biphenyl] -4-yl-κ -C3 biphenyl] -4-yl-κ-C3.

  The preferred transition metal compound (I) used in the present invention is [N-((3- (6- (phenyl-κ-C2) pyridin-2-yl-κ-N) -naphthalen-2-yl]. ) Methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3) pyridin-2-yl] -Κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylphenyl-κ-C2) pyridine-2- Yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2) pyridine-2] -Yl-κ-N) -naphthalen-2-y ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2) pyridin-2-yl-κ-N) -naphthalene -2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-C2) pyridin-2-yl-κ-N)- Naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2) pyridin-2-yl-κ-N) -Naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-fluorophenyl-κ-C2) pyridin-2-yl-κ-N) ) -Naphthalene-2- ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-methylthiophenyl-κ-C2) pyridin-2-yl-κ-N) -naphthalene-2 -Yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2) pyridin-2-yl-κ-N) -naphthalene -2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl) -Κ-C3) pyridin-2-yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 ′, 5′-Di-tert-butyl- [1,1 ′ -Biphenyl] -4-yl-κ-C3) pyridin-2-yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (Naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- ( 2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N -(2- (6- (3,5-Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -naphthalen-2-yl) -2,6-diisopropylaniline-κ-N] dimethylhafnium Biphenyl] -4- Le-kappa-C3-biphenyl] -4-yl-kappa-C3-biphenyl] -4-yl-kappa-C3 and the like.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6-([1,1′-biphenyl] -4-yl-κ-C3))]-]. Dimethyl hafnium, [N- (2- (6- (4-methylphenyl-κ-C2)))-] dimethylhafnium, [N- (2- (6- (4-isopropylphenyl-κ-C2)))) -] Dimethylhafnium, [N- (2- (6- (4-tert-butylphenyl-κ-C2)))-] dimethylhafnium, [N- (2- (6- (4-adamantylphenyl-κ-) C2)))-] dimethylhafnium, [N- (2- (6- (4-methoxyphenyl-κ-C2)))-] dimethylhafnium, [N- (2- (6- (4-fluorophenyl- κ-C2)))-] dimethylhafnium, [N- (2- 6- (4-Methylthiophenyl-κ-C2)))-] dimethylhafnium, [N- (2- (6- (4-dimethylaminophenyl-κ-C2)))-] dimethylhafnium, [N- ( 2- (6- (3 ′, 5′-dimethyl- [1,1′-biphenyl] -4-yl-κ-C3)))-] dimethylhafnium, [N- (2- (6- (3 ′ , 5′-di-tert-butyl- [1,1′-biphenyl] -4-yl-κ-C3)))-] dimethylhafnium.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2 , 6-Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4, 6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diethyl Aniline-κ-N] dimethylhafnium, [N- ( -(6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N -(2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2 -(6- (Naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6 -(Naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (Naphthalen-1-yl-κ-C2) pi Lysine-2-yl-κ-N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) ) Pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-) C2) Pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ) -C2) Pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-) κ-C2) pyridin-2-yl-κ-N -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) ) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl- κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridine-2) -Yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) Pyridin-2-yl-κ-N) -4-methylbenz ) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4- Methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4 -Fluorobenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N)- 4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridine-2-] Yl-κ-N) -4-methoxybenzyl) -2,4,6- Li-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) ) -4-Methylbenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-) N) -4-methoxybenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ) -N) -4-fluorobenzyl -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl ) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4-methoxy Benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) -4- Fluorobenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) Phenyl) methyl) -2,6-diisop Lopylaniline-κ-N] dimethylhafnium, [N- (1- (2- (6- (naphthalen-1-yl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6 -Diisopropylaniline-κ-N] dimethylhafnium biphenyl] -4-yl-κ-C3 biphenyl] -4-yl-κ-C3 biphenyl] -4-yl-κ-C3.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl. ) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2 , 6-Dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2,4, 6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2,6-diethyl Aniline-κ-N] dimethyl Ruhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ -N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium , [N (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N -(2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [ N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium , [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N -(2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium , [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N ] Dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline- κ-N] dimethylhafnium, N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium , [N- (2- (6- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N] dimethyl Hafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butyl Aniline-κ-N] dimethylhafniu , [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline -Κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6 -Tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl ) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxy Benzyl) -2,6-dicyclohe Silaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6- Dicyclohexylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6 -Diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2, 6-diphenylaniline-κ-N] dimethylhafnium, [N- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2 , 6-Diff Phenylaniline-κ-N] dimethylhafnium, [N- (phenyl (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) phenyl) methyl) -2,6- Diisopropylaniline-κ-N] dimethylhafnium, [N- (1- (2- (6- (phenanthrene-9-yl-κ-C10) pyridin-2-yl-κ-N) phenyl) ethyl) -2, 6-diisopropylaniline-κ-N] dimethylhafnium biphenyl] -4-yl-κ-C3 biphenyl] -4-yl-κ-C3 biphenyl] -4-yl-κ-C3.

  The preferred transition metal compound (I) used in the present invention is, for example, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N). Benzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2 , 4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2 , 6-Diethylaniline-κ-N] dimethylhough [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,4,6-tri-tert-butylaniline-κ -N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-dicyclohexylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) benzyl) -2,6-diphenylaniline-κ-N] dimethyl Hafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diisopropylaniline-κ-N ] Dimethyl hafnium, [N- (2- (6- ( , 5-Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (3,5-Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2 -(6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-Di Methylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6 -(3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- ( 2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-trimethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethyl) Ruphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5 -Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3 , 5-Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diethylaniline-κ-N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [ N- (2- (6- (3,5-dimethyl Enyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium, [N- (2- ( 6- (3,5-Dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,4,6-tri-tert-butylaniline-κ-N] dimethylhafnium , [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-dicyclohexylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-dicyclohexylaniline-κ- N] dimethylhafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-dicyclohexylaniline-κ-N] dimethylhafnium, [ N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methylbenzyl) -2,6-diphenylaniline-κ-N] dimethylhafnium , [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-methoxybenzyl) -2,6-diphenylaniline-κ-N] Dimethyl hafnium, [N- (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) -4-fluorobenzyl) -2,6-diphenylaniline-κ- N] dimethylhafnium, [N- (Fe Ru (2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) methyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium, [N -(2- (6- (3,5-dimethylphenyl-κ-C2) pyridin-2-yl-κ-N) phenyl) ethyl) -2,6-diisopropylaniline-κ-N] dimethylhafnium. .

  As transition metal compound (I), the derivative | guide_body of the 3rd-10th group transition metal element of a periodic table other than the titanium derivative and zirconium derivative of the compound of the said illustration may be sufficient. However, the transition metal compound (I) is not limited to the compounds exemplified above.

[Production Method of Transition Metal Compound]
The transition metal compound used in the present invention can be produced by a known method, and the production method is not particularly limited. Below, an example of the manufacturing method of the transition metal compound (4a) included by the transition metal compound (I) used by this invention is demonstrated as an example.

  In one embodiment, a step of obtaining a ligand by a coupling reaction using the compound obtained in step (1) of obtaining a pyridine derivative, step (2) of obtaining an amine derivative, step (1) and step (2). (3) Step (4) of obtaining a transition metal compound (4a) by reacting the ligand with the transition metal compound.

<Process (1)>
The pyridine derivative (1a) can be synthesized, for example, by a method of reacting the pyridine derivative (1b) and the organometallic compound (1c).

In the reaction [A], R ^{11 to} R ¹⁷ have the same meanings as the same symbols in the general formulas (II) and (III), respectively. Z ¹ and Z ² are a hydrogen atom or a leaving group, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, tosylate group, mesylate group and triflate group. M ¹ is a hydrogen atom or a metal-containing group. Examples of the metal-containing group include boron-containing groups such as dihydroxyboron, dimethoxyboron and pinacolatoboron, tin-containing groups such as tributyltin group, chloromagnesium group, bromomagnesium group, Examples thereof include magnesium-containing groups such as magnesium iodide group, zinc-containing groups such as magnesium chloride group and magnesium bromide group, and silicon-containing groups such as trimethoxysilyl group and trifluorosilyl group.

In step (1), a so-called cross-coupling reaction can be used. A known reaction can be used for the cross-coupling reaction. For example, Suzuki-Miyaura reaction using a boron-containing group as M ¹ , Negishi reaction using a zinc-containing group, Umeda-Kosugi-Stille reaction using a tin-containing group, Tamao-Kumada-Corriu reaction using a magnesium-containing group, A coupling reaction using a silicon-containing group discovered by Oo and Hiyama is known. In addition, a coupling reaction using hydrogen as M ¹ without the above metal is also known.

  These reactions are generally performed using a catalyst. A known catalyst can be used as the catalyst, and metal catalysts represented by palladium, nickel, ruthenium, platinum and iron are particularly effective. When these catalysts are used, those in which a metal is supported on a support such as activated carbon may be used, or a metal salt may be used. In addition, a metal salt and a ligand can be used in combination, or a ligand coordinated in advance may be used. Particularly suitable metal salts include palladium chloride, palladium acetate, tris (benzylideneacetone) dipalladium, nickel chloride and the like. As ligands that improve catalytic activity by reacting with these metal salts, triphenylphosphine, tri (tert-butyl) phosphine, tri (tert-butyl) phosphine / tetrafluoroborate, tricyclohexylphosphine, tricyclohexylphosphine, Examples thereof include phosphines such as tetrafluoroborate, tri (o-tolyl) phosphine, bis (diphenylphosphino) ferrocene, dialkylbiarylphosphines (Buckwald ligand), and imidazocarbenium compounds.

  In the above reaction, 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, cesium carbonate, potassium fluoride, barium hydroxide, Alkali metal or alkaline earth metal salts such as sodium alkoxide, potassium alkoxide, magnesium hydroxide, magnesium alkoxide, potassium hydrogen atom, sodium hydrogen atom; diethylamine, ammonia, pyrrolidine, piperidine, aniline, methylaniline, triethylamine, lithium diisopropyl Nitrogenous bases such as amide and sodium amide; organoalkali metal compounds such as butyllithium, methyllithium and phenyllithium; methylmagnesium chloride and methylmagnesium Romido include Grignard reagents such as phenyl magnesium chloride.

  Moreover, you may use a solvent as needed. Although there is no restriction | limiting in particular in the solvent to be used, Aliphatic hydrocarbons, such as pentane, hexane, heptane, cyclohexane, decalin; Aromatic hydrocarbons, such as benzene, toluene, 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 and acetonitrile, nitriles or nitrogen-containing compounds; methanol, ethanol, n-propanol, isopropanol, n-butanol, isopropanol, ethylene glycol, Alcohols such as xylethanol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, N-methylpyrrolidone; dimethyl sulfoxide; sulfur-containing compounds such as carbon disulfide; acetone And organic solvents such as ketones such as methyl ethyl ketone; non-organic solvents such as water and ionic liquids; or solvents obtained by mixing two or more of these.

Moreover, you may use phase transfer catalysts, such as ammonium salt, as needed.
Moreover, reaction temperature becomes like this. Preferably it is -100-300 degreeC, More preferably, it is 30-200 degreeC.

When a hydrogen atom is used as Z ¹ , for example, Eur. J. et al. Org. Chem. It may be changed to a leaving group such as a halogen atom by the method described in 2002, 3375-3383.

<Process (2)>
The amine derivative (2a) can be produced by dehydration condensation of the corresponding aldehyde and primary amine followed by a reduction reaction.

In the reaction [B], R ^{18 to} R ²¹ and R ^{26 to} R ³⁰ are respectively synonymous with the same symbols in the general formulas (IV) and (VII)), and M ² is synonymous with M ¹ described above.

The substituent on M ² of the amine derivative (2a) may differ from (2b) depending on the reaction conditions. For example when using dihydroxyboron containing group as M ² in (2b), the use of methanol as a reaction solvent, the M ² (2a) wherein it may become dimethoxy boric containing group. Further, a compound obtained by dehydration condensation between a dihydroxyboron group and a nitrogen atom and cyclization within the molecule, a multimer obtained by dehydration condensation between molecules, and the like can be considered, but there is no particular limitation.

  In the dehydration condensation reaction, a catalyst may be used as necessary. Examples of the catalyst include magnesium, calcium, lithium, zinc, aluminum, titanium, iron, zirconium, hafnium, boron, tin, rare earth halides, triflate, alumina, silica gel and other Lewis acids, sulfuric acid, phosphoric acid, acetic acid, Examples include acids such as trifluoroacetic acid, trifluoromethanesulfonic acid, and paratoluenesulfonic acid.

  It is also effective to remove water produced by the condensation reaction. Examples of the method for removing water include a method using an azeotropic phenomenon with a solvent and a method using a dehydrating agent. There are no particular restrictions on the dehydrating agent, but compounds that form hydrates such as magnesium sulfate and sodium sulfate, those that adsorb water on the pores and surfaces of molecular sieves, zeolite, silica gel, etc., acetic anhydride, The compound which can remove a water | moisture content by reacting with water, such as phosphorus oxide, is mentioned.

Examples of the solvent include the above-mentioned solvents, and there is no particular limitation as long as the reaction is not inhibited.
Moreover, reaction temperature becomes like this. Preferably it is -100-300 degreeC, More preferably, it is 30-200 degreeC.

In the reduction reaction, examples of the reducing agent include metal hydride compounds, hydrogen, hydrazine, formic acid and the like. These reducing agents are not particularly limited, but examples of the metal hydride compound include lithium aluminum hydride, sodium borohydride, lithium borohydride, zinc borohydride, borane, sodium cyanoborohydride, diisobutylaluminum hydride, Red-Al, triethylhydrosilane, etc. are mentioned. When the catalytic reduction method is used, a compound containing palladium, nickel, rhodium, ruthenium, platinum, titanium, or the like can be used as a catalyst.
Examples of the solvent include the above-mentioned solvents, and there is no particular limitation as long as the reaction is not inhibited.
Moreover, reaction temperature becomes like this. Preferably it is -100-300 degreeC, More preferably, it is 30-200 degreeC.

<Process (3)>
The ligand (3a) can be produced from the compounds obtained in the steps (1) and (2) using the cross-coupling reaction [C].
In the formula [C], M ² and R ^{11 to} R ²¹ and R ^{26 to} R ³⁰ are respectively synonymous with the same symbols in the general formulas (II), (III), (IV), and (VII).
The conditions described in the step (1) can be used for the cross coupling reaction.

<Process (4)>
The transition metal compound (4a) included in the transition metal compound (I) can be synthesized according to the formula.

In the formula [D], M and R ^{11 to} R ³⁰ are the same as the same symbols in the general formulas (I), (II), (III), (IV), and (VII), respectively, and a plurality of Z Are each independently a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordination with a lone pair, and k is an integer of 2-6. The atoms or groups listed as M and Z are the same as M and L described in the section of the general formula (I), respectively.

  Examples of the compound (4b) include divalent or trivalent chromium fluoride, chloride, bromide and iodide; divalent or trivalent iron fluoride, chloride, bromide and iodide; divalent, trivalent or Tetravalent vanadium fluoride, chloride, bromide and iodide; trivalent or tetravalent titanium fluoride, chloride, bromide and iodide; tetravalent zirconium fluoride, chloride, bromide and iodide; tetravalent Hafnium fluoride, chloride, bromide and iodide, tetrabenzyl titanium, tetrabenzyl zirconium, tetrabenzyl hafnium, tetrakis (trimethylsilylmethylene) titanium, tetrakis (trimethylsilylmethylene) zirconium, tetrakis (trimethylsilylmethylene) hafnium, dibenzyldichlorotitanium Dibenzyldi Rorozirconium, dibenzyldichlorohafnium, amide salts of titanium, zirconium, hafnium; or complexes of these with ethers such as tetrahydrofuran, diethyl ether, dioxane or 1,2-dimethoxyethane, and nitrogen-containing compounds such as pyridine A complex.

  In the above reaction, a base may be used. Examples of the alkali metal include lithium, sodium, and potassium; examples of the hydrogen atom alkali metal include sodium hydrogen atom and potassium hydrogen atom; and examples of the alkali metal alkoxide include sodium methoxide and potassium. Examples include ethoxide, sodium ethoxide, potassium tert-butoxide, etc .; examples of organic alkali metals include methyl lithium, butyl lithium, and phenyl lithium; examples of organic alkaline earth metals include methyl magnesium halide, butyl magnesium. Halide, phenylmagnesium halide, benzylmagnesium halide, organic amine compounds such as diethylamine, ammonia, pyrrolidine, piperidine, aniline, methylaniline, triethylamine, Um diisopropylamide, sodium amide or the like hail like, or may be used in combination of two or more of these.

  When a base is used, the base may be added after the ligand and (4b) have been mixed in advance, or the ligand or (4b) and the base may be reacted in advance. These steps can be divided into a plurality of times and can be arbitrarily combined.

  The reaction between the ligands (3a) and (4b) is preferably a molar ratio (ligand (3a) :( 4b)) = 10: 1 to 1:10, more preferably 2: 1 to 1: 2, particularly preferably 1.2: 1 to 1: 1.2. When a base is used, the molar ratio (base: (4b)) = 40: 1 to 1: 5, more preferably 10: 1 to 1: 3, particularly preferably 5: 1 to 1: 1. Perform in step 2. The reaction temperature is preferably −100 to 200 ° C., more preferably −80 to 120 ° C.

The transition metal compound (4a) obtained by the above reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. The transition metal compound (4a) 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, elemental analysis, and single crystal structure analysis. The

The transition metal compound (4a) obtained by the above reaction can be isolated and purified by methods such as extraction, recrystallization and sublimation. The transition metal compound (4a) obtained by such a method can be identified by using analytical techniques such as proton nuclear magnetic resonance spectrum, ¹³ C-nuclear magnetic resonance spectrum, mass spectrometry, crystal structure analysis and elemental analysis. it can.
The transition metal compound (I) can also be handled in the same manner as the transition metal compound (4a).

[Olefin polymerization catalyst]
The olefin polymerization catalyst used in the present invention contains a transition metal compound (I) represented by the general formula (I).
The olefin polymerization catalyst used in the present invention further comprises:
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (I) to form an ion pair. It is preferable to contain a seed compound (hereinafter also referred to as “compound (B)”).

The olefin polymerization catalyst of the present invention may further contain (C) a carrier, if necessary. Moreover, the catalyst for olefin polymerization of this invention can also contain (D) organic compound component further as needed.
Hereinafter, each component other than the transition metal compound (I) that can be included in the olefin polymerization catalyst will be specifically described.

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

(B-1a): R ^a _m Al (OR ^b ) _n H _p X _q
In formula (B-1a), R ^a and R ^b 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, n is a number satisfying 0 ≦ n <3, p is 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): M ^a AlRa ₄
Wherein (B-1b), M ^a is Li, Na or K, Ra is 15 carbon atoms, preferably 1-4 hydrocarbon group. Examples of the complex alkylated product (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(B-1c): R ^a R ^b M ³
In formula (B-1c), R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ 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) and organozinc (B-1c) are preferred.
An organometallic compound (B-1) may be used individually by 1 type, and may use 2 or more types together.

<< Organic aluminum oxy compound (B-2) >>
As the organoaluminum oxy compound (B-2), for example, a conventionally known aluminoxane may be used, which is insoluble or hardly soluble in benzene as exemplified in JP-A-2-78687. It may be a compound. 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) A compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first 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 in which water, ice or water vapor is directly applied to 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) A non-hydrolytic reaction such as a thermal decomposition reaction is performed on a compound formed by reacting an organic aluminum such as a trialkylaluminum with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, ketone, or carboxylic acid. 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 is particularly preferable.

  Other 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 can be prepared by the methods listed in US Pat. Nos. 4,960,878 and 5,041,584. In addition, aluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and having R as an isobutyl group are commercially produced under the names MMAO and TMAO.

  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, aliphatic hydrocarbons and It has the feature of being soluble in alicyclic hydrocarbons.

Further, as the organoaluminum oxy compound (B-2), for example, an organoaluminum oxy compound containing a boron atom, and those exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010 An aluminoxane containing a halogen and an ionic aluminoxane as exemplified in WO2003 / 082879 can also be mentioned.
A compound (B-2) may be used individually by 1 type, and may use 2 or more types together.

<< Compound (B-3) which reacts with transition metal compound (I) to form an ion pair >>
As the compound (B-3) (hereinafter also referred to as “ionic compound (B-3)”) which reacts with the transition metal compound (I) to form an ion pair, for example, JP-A-1-501950 JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US5321106, etc. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
The ionic compound (B-3) is preferably a compound represented by the general formula (B-3a).

In the 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 the ammonium cation 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 cation 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 Re ⁺ , 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 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) bore 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, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate , Dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate include dioctadecyl methyl ammonium.

  Examples of the N, N-dialkylanilinium salt 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.

In addition, as the ionic compound (B-3), an ionic compound disclosed by the present applicant (eg, Japanese Patent Application Laid-Open No. 2004-51676) can be used without limitation.
The ionic compound (B-3), wherein (B-3a), it is preferred that R ^f to R ⁱ is pentafluorophenyl group.

An ionic compound (B-3) may be used individually by 1 type, and may use 2 or more types together.
When the compound (B) is contained in an olefin polymerization catalyst, in addition to the (B-1) organometallic compound, the (B-2) organoaluminum oxy compound and (B-3) transition It is a preferred embodiment that it contains at least one compound selected from compounds that react with the metal compound (I) to form ion pairs.

<Carrier (C)>
Examples of the carrier (C) include inorganic or organic compounds and granular or fine particle solids. The transition metal compound (I) may be 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, ThO ₂ , or a composite containing these. Mixtures can be used. For example, natural or synthetic zeolite, 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 drying and / or baking 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 constituted 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. Further, 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 thereof 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 treatment such as a surface treatment for removing 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. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation.

Examples of the guest compounds to be intercalated include, for example, TiCl _4, ZrCl ₄ cationic inorganic compounds such _{as, Ti (OR) 4, Zr} (OR) 4, PO (OR) 3, B (OR) 3 or the like of metal Metal hydroxide such as alkoxide (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Examples include physical ions. These compounds may be used individually by 1 type, and may use 2 or more types together. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group or the like). 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 carriers (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, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, vinylcyclohexane and styrene are mainly used. 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 case of olefin polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound (I), 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 of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) a catalyst component having component (A) supported on component (C);
A method in which component (B) is added to the polymerization vessel in any order.
(4) a catalyst component carrying component (B) on component (C);
A method of adding the component (A) 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 a polymerization vessel.

  In each of the methods (1) to (5), the component (D) may be added in any order as necessary. In each of the above methods (2) to (5), at least two of the catalyst components may be contacted in advance. In the above methods (4) and (5) in which the component (B) is supported, the component (B) that is not supported may be added in any order as necessary. In this case, the component (B) may be the same or different. Further, 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.

  Further, as with the transition metal compound (I), an olefin polymerization catalyst having a transition metal-carbon bond in a polydentate ligand is known to be an active species when an olefin is inserted into the ligand ( J. AM. CHEM. SOC. 2007, 129, 7831-7840). Like the reaction of this example, after inserting an olefin in a ligand beforehand, you may add to a polymerization device as it is, or you may add to a polymerization device after isolating and refine | purifying.

[Olefin polymer production method]
The method for producing an olefin polymer according to the present invention comprises at least one olefin selected from ethylene and an α-olefin having 3 to 100,000 carbon atoms, preferably ethylene and 3 to 3 carbon atoms, in the presence of the above-mentioned catalyst for olefin polymerization. A step of polymerizing at least one olefin selected from 30 α-olefins. Here, “polymerization” is used as a generic term for homopolymerization and copolymerization. In addition, “polymerize olefin in the presence of olefin polymerization catalyst” means that each component of the olefin polymerization catalyst is added to the polymerization vessel by any method as in the above methods (1) to (5). And an embodiment of polymerizing 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. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

  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.
Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of usually 1 to 50,000, preferably Can be used in an amount of 5 to 20,000, particularly preferably 10 to 10,000. Component (B-2) has a molar ratio [Al / M] of aluminum atoms in component (B-2) to all transition metal atoms (M) in component (A) of usually 2 to 5,000, preferably Can be used in an amount of 5 to 2,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) of usually 1 to 10,000, preferably 1 It can be used in such an amount that it becomes ˜2000.

  When component (B) is used as a chain transfer agent, the molar ratio [olefin / (B)] of the olefin monomer and component (B) contained in the polymer to be produced is usually 1 to 1000000, preferably 3 to The amount can be 10,000, particularly preferably 10 to 5,000.

  In this case, the chain transfer agent is preferably an organoaluminum compound, an organozinc compound, or an organomagnesium compound among the components (B) described above, and an organoaluminum compound is particularly preferred from the viewpoint of economy, and triethylaluminum, More preferred are isobutylaluminum, diisobutylaluminum hydride, trihexylaluminum, and trioctylaluminum.

  When component (C) is used, the weight ratio of component (A) to component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5. More preferably, it can be used in an amount of 0.001 to 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 0.8. When the component (B) is the component (B-2) in an amount of 1 to 5, the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0. When the component (B) is the component (B-3), the molar ratio (D) / (B-3)] is usually 0.01 to 10, preferably 0.00. The amount can be 1 to 5.

  In the production method of the present invention, the polymerization temperature of the olefin is usually −50 to + 200 ° C., preferably 0 to 180 ° 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 exist 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 an arbitrary 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 200 ° C., more preferably 45 to 180 ° C., and particularly preferably 50 to 180 ° C.

  Hydrogen can be said to be a preferred 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 100,000 carbon atoms, preferably ethylene and an α-olefin having 3 to 30 carbon atoms. It is at least one olefin selected, and two or more olefins can be used in combination as required.

As the α-olefin, an α-olefin having 3 to 30 carbon atoms is preferable, 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 the α-olefin include a linear or branched α-olefin. Examples of the linear or branched α-olefin 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 olefin 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.

As the olefin having a polar group, for example,
Α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride Acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, and aluminum salts;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; unsaturated glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Glycidyl;
Is mentioned.

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

  Examples of the aromatic vinyl compound include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, and the like. 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 diene and triene. It is also a preferred embodiment that polyene is used in the range of 0.0001 to 1 mol% with respect to the total olefin supplied to the polymerization reaction.

  Examples of the diene 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-non-conjugated dienes such as 9-decadiene; non-conjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene; 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 Non-conjugated trienes such as nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecandiene; and conjugated 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 or 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.

  Moreover, you may use what is called a macromer obtained by superposing | polymerizing 1 or more types of the said olefin. By using a macromer, a branched polymer can be obtained. Although there is no restriction | limiting in particular in carbon number of a macromer, 30-100,000 are preferable and 50-10000 are more preferable. The macromer may be produced in advance or may be produced in a polymerization system using a catalyst capable of producing a macromer.

  In the method for producing an olefin polymer of the present invention, at least one of the supplied olefins is more preferably 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. It is more preferable that

  The polymers produced include ethylene homopolymerization, ethylene / propylene copolymer, propylene homopolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymerization, ethylene / 1-octene copolymerization, and ethylene / propylene / 5-ethylidene-2-norbornene copolymerization are preferred.

The weight average molecular weight in terms of polystyrene measured by GPC of the polymer produced by the production method of the present invention is not particularly limited, but is usually in the range of 10,000 to 5,000,000, preferably 50,000 to 2,000,000. 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 olefin polymerization method of the present invention is 1.0 to 5.0, preferably Is from 1.2 to 4.5, more preferably from 1.5 to 3.5, 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]
1. Ethylene content of ethylene / propylene copolymer By using Fourier transform infrared spectrophotometer FT / IR-610 manufactured by JASCO Corporation, the area near roll vibration 1155 cm ⁻¹ based on methyl group of propylene and C—H stretching vibration Absorbance in the vicinity of overtone absorption 4325 cm ⁻¹ was determined and calculated from the ratio by a calibration curve (prepared using a standard sample standardized by ¹³ C-NMR).

2. Weight average molecular weight (Mw), number average molecular weight (Mn)
Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn) by moving 500 μl of a sample solution having a concentration of 0.15 (w / v)% at a flow rate of 1.0 ml / min using Alliance GPC2000 manufactured by Waters. Went.
Separation columns: TSKgel GMH6-HT and TSKgel GMH6-HTL
(Two columns each having an inner diameter of 7.5 mm and a length of 300 mm were used.)
-Column temperature: 140 ° C
・ Mobile phase: o-dichlorobenzene (containing 0.025 wt% dibutylhydroxytoluene)
-Detector: Polystyrene made by Tosoh Corporation was used as a differential refractometer standard material. For polyethylene, polypropylene, and ethylene / propylene copolymers, the molecular weight of each polymer was calculated using a general calibration method. The Mark-Houwink coefficient was as follows. For the ethylene / octene copolymer and the ethylene / propylene / 5-ethylidene-2-norbornene copolymer, values in terms of polystyrene were described.
Coefficient of polystyrene (PS) K _PS = 1.38 × 10 ⁻⁴ , α _PS = 0.70
(J. V. Dawkins, J. W. Maddock, D. J. Coupe, J. Polym. Sci., Part A-2, 8, 1803 (1970)).
Polyethylene (PE) coefficient K _PE = 5.06 × 10 ⁻⁴ , α _PE = 0.7
(J. V. Dawkins, J. W. Maddock, Eur. Polym. J., 7, 1537 (1971)).
Coefficient of polypropylene (PP) K _PP = 2.42 × 10 ⁻⁴ , α _PP = 0.707
(C. M. L. Atkinson, R. Dietz, Makromol. Chem., 177 , 213 (1976)).
The coefficient of ethylene-propylene copolymer (EPR) was calculated according to the following formula.

(W _PE is ethylene content / wt%)

3. Temperature rising elution fractionation curve (TREF curve) of block copolymer, Mw, Mn
Crystallization was performed by injecting 500 μl of a sample solution having a concentration of 0.40 (w / v)%, dissolving at 140 ° C., and cooling at −20 ° C. using a cross-fraction chromatograph CFC2 manufactured by Polymer ChAR. Fractionation in the range of -20 ° C to 140 ° C is divided every 5 ° C and moved at a flow rate of 1.0 ml / min to perform cross fractionation chromatogram (CFC) measurement. (TREF curve) was obtained. As a standard substance, polystyrene manufactured by Tosoh Corporation was used, and the molecular weight of each polymer was calculated using the above-described general-purpose calibration method. The average value calculated from ¹³ C-NMR was used for the composition of the polymer, and the same value was used for each fraction component. Fraction components with an elution amount of 0.5 wt% or less were excluded from the calculation of the average molecular weight.
Detector: Infrared spectrophotometer IR ⁴ (Polymer ChAR)
Detection wavelength: 3.42 μm (2,920 cm −1); Fixed GPC column: Shodex HTERT-806M × 3 (Showa Denko)
GPC column temperature: 140 ° C
Mobile phase: o-dichlorobenzene, dibutylhydroxytoluene contained

4). Structural analysis of block copolymer Measurement was carried out under the following conditions using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker BioSpin.
Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling pulse width: 45 °
Number of points: 64k
Observation range: 250 ppm (-55 to 195 ppm)
Repeat time: 5.5 seconds Integration count: 128 times Measurement solvent: Orthodichlorobenzene / benzene-d6 (4/1 v / v)
Sample concentration: ca. 60mg / 0.6mL
Measurement temperature: 120 ° C
Chemical shift standard: δδ signal: 29.73 ppm

5. Unsaturated bond amount of polymer <Unsaturated bond amount of polymer> Method A)
The amount of unsaturated bonds of the amorphous polymer was calculated from the ¹ H-NMR spectrum. ¹ H-NMR spectrum was measured by dissolving 20 mg of sample in 0.6 ml of deuterated chloroform, using GSH-270 manufactured by JEOL Ltd., room temperature, 45 ° pulse, repetition time of 10 seconds, and number of integrations of 128 times. did. The standard value of chemical shift was 0 ppm for tetramethylsilane. The peak of 5.05 to 4.9 ppm is vinyl group (2H), the peak of 4.9 to 4.6 ppm is vinylidene group (2H), the peak of 2 to 0.1 ppm is saturated bond (2H per carbon The number of unsaturated bond substituents per 1000 carbons was calculated from the area ratio for peaks having an S / N ratio of 5 or more.

<Unsaturated bond amount of polymer> Method B)
The amount of unsaturated bonds of the polymer was calculated from ¹ H-NMR spectrum. ^{The 1} H-NMR spectrum was obtained by dissolving 20 mg of a sample in 0.6 ml of deuterated o-dichlorobenzene, using an ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL, and using a 120 ° C., 45 ° pulse, and a repetition time of 7 Measured at a second of 512 times. The standard value of chemical shift was set to 7.1 ppm of residual protons of deuterated o-dichlorobenzene. The peak of 4.95 to 4.75 ppm is vinyl group (2H), the peak of 4.7 to 4.5 ppm is vinylidene group (2H), the peak of 2.8 to 0 ppm is saturated bond (2H per carbon The number of unsaturated bond substituents per 1000 carbons was calculated from the area ratio for peaks having an S / N ratio of 5 or more.

6). Melting point (Tm)
Using an EXSTAR DSC6000, a melting point of SII Nanotechnology, an ethylene-propylene block copolymer, in a nitrogen atmosphere (30 mL / min), a sample of about 6 mg was heated to 230 ° C. and held for 10 minutes, then 10 ° C./minute At 30 ° C. The peak peak of the peak derived from crystallization observed at this time was defined as the crystallization temperature Tc. After maintaining at 30 ° C. for 1 minute, the melting point (Tm) was calculated from the peak apex of the crystal melting peak when the temperature was raised to 230 ° C. at 10 ° C./min.

Melting point of ethylene-tetracyclododecene copolymer EXSTAR DSC6000 manufactured by SII Nanotechnology Inc. was used, and a temperature of about 7 mg was raised to 230 ° C. and held for 10 minutes under a nitrogen atmosphere (30 mL / min). The solution was cooled to -20 ° C at / min. After maintaining at −20 ° C. for 5 minutes, the glass transition temperature (Tg) was calculated from the inflection point derived from the glass transition point when the temperature was raised to 230 ° C. at 10 ° C./min.

7). Mn (exp) / Mn (theor)
Mn (exp) and Mn (theor) were calculated according to the following, and their ratio was determined.
Mn (exp): Using the value of the number average molecular weight Mn obtained by GPC as described above Mn (theor) = yield of polymer (g) / ([Al] × 3 + [transition metal compound])
[Al]: Amount of aluminum compound used (mol)
[Transition metal compound]: amount of transition metal compound used (mol)
If Mn (exp) / Mn (theor) = 1, this indicates that a compound (polymer) in which 3 mol of polymer is bonded per 1 mol of Al atom is generated by chain transfer reaction, and Mn (exp) / Mn (theor) = 3 indicates that a compound (polymer) in which 1 mol of polymer is bonded per 1 mol of Al atom is formed. A large value of Mn (exp) / Mn (theor) indicates that the efficiency of the chain transfer reaction to the chain transfer agent (in this case, the aluminum compound) is low. Although there is no restriction | limiting in particular about Mn (exp) / Mn (theor) in the case of superposing | polymerizing using an organometallic compound (B-1) as a chain transfer agent, From a viewpoint of the use efficiency of a chain transfer agent, Mn (exp) / Mn (theor) is preferably 10 or less, and more preferably 5 or less.

8). Identification of structure and purity of compound and catalyst The structure and purity of the compound and catalyst obtained in Examples and the like were 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 structural analysis (D8 VENTURE, Cu source manufactured by Bruker AXS Co., Ltd.) and the like.

Triisobutylaluminum (TIBAL, purity 97 wt%, manufacturer reported value), MMAO-3A hexane solution manufactured by Tosoh Finechem Co., Ltd., and triphenylcarbenium tetrakis (pentafluorophenyl) borate manufactured by Asahi Glass Co., Ltd. were used. Triisobutylaluminum was used in advance as a 1 mol / l toluene solution, and triphenylcarbenium tetrakis (pentafluorophenyl) borate was used as a 5 mmol / l toluene solution.
Unless otherwise specified, all examples were performed using a dry solvent under a dry nitrogen atmosphere.

[Synthesis of transition metal compounds]
[Example 1A] Synthesis of transition metal compound A (1) Synthesis of pyridine derivative A

Under a nitrogen atmosphere, a 500 ml four-necked flask was charged with 80 ml of hexane and 7.33 g (82.3 mmol) of dimethylaminoethanol. To this solution, a hexane solution of n-butyllithium (1.64 M, 100.5 ml, 165 mmol) was added dropwise over 1 hour in an ice-water bath. After stirring for 30 minutes, 4.26 g (27.5 mmol) of 2-phenylpyridine was added dropwise over 50 minutes. After stirring for 1 hour and 15 minutes, a hexane solution (100 ml) of 31.8 g (95.8 mmol) of carbon tetrabromide was added dropwise over 2 hours in a dry ice / methanol bath. After stirring for 1 hour, the temperature was slowly returned to room temperature and stirred for 16 hours. Water was charged into the reaction solution, and the organic layer was separated. The organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. After purification by column chromatography, recrystallization using methanol gave the title compound as a powder. Yield 2.21 g, yield 34%.
¹ H-NMR (CDCl ₃ ) δ: 7.9-7.97 (1H, m), 7.97-7.94 (1H, m), 7.67 (1H, dd, J = 7.9, 1.0 Hz), 7.57 (1H, t, J = 7.7 Hz), 7.49-7.42 (3H, m), 7.39 (1H, dd, J = 7.7, 0 .8 Hz).

  (2) Synthesis of boronic acid derivative A

Under a nitrogen atmosphere, in a 200 ml eggplant flask equipped with a fractionator, 5.07 g (33.8 mmol) of 2-formylphenylboronic acid, 7.17 g (40.5 mmol) of 2,6-diisopropylaniline, 9.86 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.81 g (101 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After the solvent was distilled off under reduced pressure, 85 ml of 2N hydrochloric acid was added. Neutralized with 10% aqueous sodium hydroxide and filtered to obtain a solid. The obtained solid was washed with water and methanol and then dried under reduced pressure to obtain a white powder. Yield 5.61 g.
In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand A

Under a nitrogen atmosphere, tris (benzylideneacetone) dipalladium 32.1 mg (0.0351 mmol), tritert-butylphosphine 19.3 mg (0.0954 mmol), pyridine derivative A 0.546 g (2.33 mmol) in a 50 ml Gildar flask Boronic acid derivative A 0.728 g (2.34 mmol), THF 20 g, 5N sodium hydroxide aqueous solution 1.52 g were charged. The mixture was stirred for 18 hours under reflux, and then returned to room temperature. 150 ml of toluene was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, it was filtered using a small amount of silica gel. After the solvent was distilled off, methanol was added and cooled. The precipitated solid was removed by filtration, washed with methanol, and dried under reduced pressure to obtain the desired product. Yield 0.752g, 77% yield.
They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (DMSO-d ₆ ) δ: 8.12-7.9 (4H, m), 7.55-7.32 (8H, m), 6.99-6.89 (3H, m) , 4.06-3.94 (3H, m), 3.15-3.00 (2H, m), 0.93 (12H, d, J = 6.6 Hz).
FD-MS m / z = 420.3 (M +)

  (4) Synthesis of transition metal compound A

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.300 g (0.714 mmol) of ligand A, 0.229 g (0.714 mmol) of hafnium tetrachloride and 17.842 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 1.0 ml, 3.0 mmol) was added over 10 minutes. The mixture was stirred for 16 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 20 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was washed with toluene and dried under reduced pressure to obtain the desired product. Yield 0.291 g, 65% yield.
They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 8.17-8.11 (1H, m), 7.74 (1H, dd, J = 7.7, 0.8 Hz), 7.65-7 .59 (1H, m), 7.37 (1H, dd, J = 8.2, 1.0 Hz), 7.29-7.14 (4H, m), 7.12-6.96 (4H M), 6.89 (1H, dd, J = 7.6, 1.6 Hz), 6.80 (1H, dd, J = 7.6, 1.0 Hz), 4.37-4. 26 (2H, m), 4.02 (1H, d, J = 11.5 Hz), 2.73 (1H, sept, J = 6.6 Hz), 1.51 (3H, d, J = 6) .6 Hz), 1.47 (3H, d, J = 6.6 Hz), 0.78 (3H, d, J = 6.6 Hz), 0.61 (3H, s) , 0.40 (3H, d, J = 6.6 Hz), −0.31 (3H, s). (See Figure 1)

[Example 1B] Synthesis of transition metal compound B (1) Synthesis of pyridine derivative B

Under a nitrogen atmosphere, tetrakis (triphenylphosphine) palladium 0.693 g (0.599 mmol), naphthylboronic acid 2.50 g (14.5 mmol), 2,6-dibromopyridine 5.35 g (22) .6 mmol), 7.08 g (22.4 mmol) of barium hydroxide octahydrate and 50 ml of dimethoxyethane / water (2/1) were charged and stirred for 15 hours under reflux. 150 ml of hexane was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. Purification by column chromatography gave the title compound. Identified by ¹ H-NMR. Yield 2.81 g, 68% yield.
¹ H-NMR (CDCl ₃ ) δ: 8.10-8.03 (1H, m), 7.94-7.87 (2H, m), 7.71-7.47 (7H, m).

  (2) Synthesis of boronic acid derivative A

Under a nitrogen atmosphere, in a 200 ml eggplant flask equipped with a fractionator, 5.07 g (33.8 mmol) of 2-formylphenylboronic acid, 7.17 g (40.5 mmol) of 2,6-diisopropylaniline, 9.86 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.81 g (101 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After the solvent was distilled off under reduced pressure, 85 ml of 2N hydrochloric acid was added. Neutralized with 10% aqueous sodium hydroxide and filtered to obtain a solid. The obtained solid was washed with water and methanol and then dried under reduced pressure to obtain a white powder. Yield 5.61 g.
In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand B

In a 50 ml Gildar flask under nitrogen atmosphere, 57.7 mg (0.0630 mmol) of tris (benzylideneacetone) dipalladium, 34.4 mg (0.170 mmol) of tri-tert-butylphosphine, 1.19 g (4.18 mmol) of pyridine derivative B Boronic acid derivative A 1.30 g, THF 30 ml, potassium fluoride 0.801 g (13.8 mmol) were charged, and the mixture was stirred at 50 ° C. for 18 hours and under reflux for 2 hours. After charging 2.80 ml of 5N aqueous sodium hydroxide solution and stirring for 20 hours, the temperature was returned to room temperature. 150 ml of toluene was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, it was filtered using a small amount of silica gel. After the solvent was distilled off, methanol was added and cooled. The precipitated solid was removed by filtration, washed with methanol, and dried under reduced pressure to obtain the desired product. Yield 1.79 g, 91% yield.
They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.07 (1H, d, J = 8.2 Hz), 7.94-7.86 (3H, m), 7.71 (1H, dd, J = 7 .1, 1.2 Hz), 7.61-7.42 (5H, m), 7.39-7.28 (4H, m), 7.01 (3H, s), 4.16 (2H, d, J = 7.3 Hz), 3.77 (1H, t, J = 7.3 Hz), 3.11 (2H, sept, J = 6.9, 6.9, 6.9 Hz), 0.98 (12H, d, J = 6.9 Hz).
FD-MS m / z = 470.3 (M +)

  (4) Synthesis of transition metal compound B

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.400 g (0.850 mmol) of ligand B, 0.273 g (0.852 mmol) of hafnium tetrachloride and 17.831 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 1.25 ml, 3.75 mmol) was added over 10 minutes. The mixture was stirred for 23 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 40 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was washed with hexane and dried under reduced pressure to obtain the desired product. Yield 0.319 g, yield 54%.
They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 8.32 (1H, d, J = 8.6 Hz), 8.25 (1H, d, J = 7.6 Hz), 7.83 (1H, d, J = 7.9 Hz), 7.70 (1H, d, J = 6.9 Hz), 7.61 (1H, dd, J = 8.1, 1.5 Hz), 7.50 ( 1H, d, J = 7.6 Hz), 7.36-7.17 (4H, m), 7.12-6.95 (4H, m), 6.89 (1H, dd, J = 7. 7, 1.5 Hz), 6.79 (1H, dd, J = 7.6, 1.0 Hz), 4.34-4.23 (2H, m), 4.08 (1H, d, J = 11.5 Hz), 2.47 (1H, sept, J = 6.9 Hz), 1.50 (6H, dd, J = 13.8, 6.9 Hz), 0 69 (6H, t, J = 6.3 Hz), 0.27 (3H, d, J = 6.9 Hz), -0.24 (3H, s). (See Figure 2)

[Example 1C] Synthesis of transition metal compound C (1) Synthesis of pyridine derivative C

Under a nitrogen atmosphere, in a 100 ml three-necked flask, 0.553 g (2.11 mmol) of triphenylphosphine, 0.158 g (0.704 mmol) of palladium acetate, 3.12 g (14.1 mmol) of phenanthrylboronic acid, 2, 6-dibromopyridine (5.02 g, 21.2 mmol), barium hydroxide octahydrate (6.66 g, 21.1 mmol) and dimethoxyethane / water (2/1) (60 ml) were charged, and the mixture was refluxed for 24 hours. Stir. Toluene (180 ml) was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying over magnesium sulfate, purification by column chromatography gave the title compound. Yield 3.11 g, 66% yield. Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 8.74 (2H, dd, J = 14.5, 8.2 Hz), 8.05 (1H, dd, J = 8.2, 1.5 Hz), 7.93 (1H, dd, J = 7.9, 1.6 Hz), 7.87 (1H, s), 7.74-7.56 (7H, m).

  (2) Synthesis of boronic acid derivative A

Under a nitrogen atmosphere, in a 200 ml eggplant flask equipped with a fractionator, 5.07 g (33.8 mmol) of 2-formylphenylboronic acid, 7.17 g (40.5 mmol) of 2,6-diisopropylaniline, 9.86 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.81 g (101 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After the solvent was distilled off under reduced pressure, 85 ml of 2N hydrochloric acid was added. Neutralized with 10% aqueous sodium hydroxide and filtered to obtain a solid. The obtained solid was washed with water and methanol and then dried under reduced pressure to obtain a white powder. Yield 5.61 g.
In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand C

In a 50 ml Gildar flask under nitrogen atmosphere, 26.5 mg (0.0289 mmol) of tris (benzylideneacetone) dipalladium, 15.9 mg (0.0786 mmol) of tri-tert-butylphosphine, 0.644 g (1.93 mmol) of pyridine derivative C Then, 0.600 g of boronic acid derivative A, 20.0 g of THF, and 1.21 g of 5N aqueous sodium hydroxide solution were charged and stirred for 19 hours under reflux. 150 ml of toluene was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, it was filtered using a small amount of silica gel. After the solvent was distilled off, methanol was added and cooled. The precipitated solid was removed by filtration, washed with methanol, and dried under reduced pressure to obtain the desired product. Yield 0.914 g, 91% yield.
They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.74 (1H, d, J = 8.2 Hz), 8.69 (1H, d, J = 8.2 Hz), 8.07 (1H, dd, J = 8.4, 0.8 Hz), 7.96-7.91 (2H, m), 7.87 (1H, dd, J = 7.9, 1.3 Hz), 7.69-7 .54 (6H, m), 7.41-7.28 (4H, m), 7.00 (3H, s), 4.19 (2H, d, J = 6.3 Hz), 3.82 ( 1H, t, J = 7.4 Hz), 3.12 (2H, sept, J = 6.9 Hz), 0.97 (12H, d, J = 6.9 Hz).
FD-MS m / z = 520.3 (M +)

  (4) Synthesis of transition metal compound C

Under a nitrogen atmosphere, a 30 ml Schlenk tube) was charged with 0.400 g (0.769 mmol) of ligand C, 0.246 g (0.768 mmol) of hafnium tetrachloride and 18.0 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 1.10 ml, 3.30 mmol) was added over 10 minutes. The mixture was stirred for 16 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 50 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was washed with toluene and dried under reduced pressure to obtain the desired product. As a result of NMR analysis, 2.6 wt% toluene was contained. Yield 0.467 g, 81% yield. They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 8.48-8.31 (4H, m), 7.74 (1H, dd, J = 7.7, 0.8 Hz), 7.61 (1H , Dd, J = 8.1, 0.8 Hz), 7.46-7.39 (2H, m), 7.32-7.22 (4H, m), 7.13-6.970 (4H) M), 6.85 (1H, d, J = 7.6 Hz), 6.73 (1H, dd, J = 7.6, 1.0 Hz), 4.49 (1H, d, J = 11.5 Hz), 4.38 (1H, sept, J = 6.6 Hz), 4.10 (1H, d, J = 11.9 Hz), 3.21 (1H, sept, J = 6. 6 Hz), 1.53 (3H, d, J = 6.6 Hz), 1.51 (3H, d, J = 6.6 Hz), 0.92 (3H d, J = 6.6 Hz), 0.44 (3H, s), 0.31 (3H, d, J = 6.6 Hz), -0.03 (3H, s). (See Figure 3)

[Example 1D] Synthesis of transition metal compound D (1) Synthesis of pyridine derivative D

Under a nitrogen atmosphere, in a 100 ml three-necked flask, 0.500 g (1.91 mmol) of triphenylphosphine, 0.142 g (0.634 mmol) of palladium acetate, 2.76 g (13.9 mmol) of biphenylboronic acid, 2,6 -Charge 5.00 g (21.1 mmol) of dibromopyridine, 6.65 g (21.1 mmol) of barium hydroxide octahydrate and 50 ml of dimethoxyethane / water (2/1), and stir at reflux for 19 hours. did. 150 ml of toluene was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solution was concentrated. The precipitated solid was removed by filtration to give the title compound. Yield 2.36 g, 55% yield. Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 8.08 (2H, dt, J = 8.6, 2.0 Hz), 7.76-7.58 (6H, m), 7.50-7.35 (4H, m).

  (2) Synthesis of boronic acid derivative B

In a 200 ml eggplant flask equipped with a fractionator under a nitrogen atmosphere, 5.30 g (35.3 mmol) of 2-formylphenylboronic acid, 7.47 g (42.2 mmol) of 2,6-diisopropylaniline, 9.88 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.96 g (105 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After distilling off the solvent under reduced pressure, 90 ml of 2N hydrochloric acid was added. Neutralization with 10% aqueous potassium hydroxide and filtration gave a solid. The obtained solid was washed with water and then dried under reduced pressure to obtain the desired product. Yield 11.21 g.
In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand D

Under a nitrogen atmosphere, in a 50 ml Gildar flask, 36.0 mg (0.0289 mmol) of tris (benzylideneacetone) dipalladium, 22.4 mg (0.111 mmol) of tri-tert-butylphosphine, 0.800 g (2.58 mmol) of pyridine derivative D Then, 0.805 g of boronic acid derivative B, 20.1 g of THF, and 1.57 g of 5N aqueous sodium hydroxide solution were charged, and the mixture was stirred for 19.5 hours under reflux. Hexane 150 ml and toluene 100 ml were added, and the organic layer was washed with water and saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. After washing with ethanol, about 3 ml of toluene was added. Insolubles were removed by filtration and concentrated. After washing with ethanol, the desired product was obtained by drying under reduced pressure. Yield 0.644 g, yield 50%. They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.15 (2H, dt, J = 8.6, 2.0 Hz), 7.87 (1H, t, J = 7.7 Hz), 7.79 ( 1H, dd, J = 7.9, 1.0 Hz), 7.68 (1H, t, J = 2.0 Hz), 7.66-7.60 (3H, m), 7.51-7 .24 (8H, m), 7.02 (3H, s), 4.15 (2H, s), 3.85 (1H, s), 3.14 (2H, sept, J = 7.1 Hz) , 1.04 (12H, d, J = 7.1 Hz).
FD-MS m / z = 496.3 (M +)

  (4) Synthesis of transition metal compound D

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.300 g (0.588 mmol) of ligand D, 0.188 g (0.588 mmol) of hafnium tetrachloride, and 18.0 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 0.82 ml, 2.5 mmol) was added over 10 minutes. The mixture was stirred for 17 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was washed with toluene and dried under reduced pressure to obtain the desired product. Yield 0.297 g, yield 72%. They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 8.53 (1H, d, J = 2.0 Hz), 7.77-7.71 (2H, m), 7.52-7.47 (3H , M), 7.42 (1H, dd, J = 8.2, 1.0 Hz), 7.30-6.97 (9H, m), 6.89 (1H, dd, J = 7.9) , 1.6 Hz), 6.82 (1H, dd, J = 7.6, 1.0 Hz), 4.39-4.29 (2H, m), 4.04 (1H, d, J = 11.2 Hz), 2.81 (1H, sept, J = 6.9 Hz), 1.52-1.47 (6H, m), 0.81 (3H, d, J = 6.9 Hz) , 0.68 (3H, s), 0.48 (3H, d, J = 6.6 Hz), −0.27 (3H, s). (See Figure 4)

[Example 1E] Synthesis of transition metal compound E (1) Synthesis of pyridine derivative E

Under a nitrogen atmosphere, in a 100 ml three-necked flask, 0.500 g (1.91 mmol) of triphenylphosphine, 0.144 g (0.641 mmol) of palladium acetate, 2.48 g (13.9 mmol) of p-tert-butylphenylboronic acid ), 2,6-dibromopyridine 5.00 g (21.1 mmol), barium hydroxide octahydrate 6.66 g (21.1 mmol), dimethoxyethane / water (2/1) 50 ml, and refluxed. Stirred under for 16 hours. 150 ml of toluene was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solution was concentrated. The product was purified by column chromatography, and the obtained compound was recrystallized from a mixed solvent of ethanol and methanol. The supernatant was concentrated and recrystallized from hexane. The obtained supernatant was concentrated and recrystallized again with methanol. The filtered solid was washed with methanol and dried under reduced pressure to obtain the title compound. Yield 0.710 g, 18% yield. Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.92 (2H, dt, J = 8.8, 2.1 Hz), 7.66 (1H, dd, J = 7.9, 0.8 Hz), 7.57 (1H, t, J = 7.7 Hz), 7.48 (2H, dt, J = 8.8, 2.1 Hz), 7.38 (1H, dd, J = 7.9, 1.0 Hz), 1.36 (9H, d, J = 5.9 Hz).

  (2) Synthesis of boronic acid derivative B

In a 200 ml eggplant flask equipped with a fractionator under a nitrogen atmosphere, 5.30 g (35.3 mmol) of 2-formylphenylboronic acid, 7.47 g (42.2 mmol) of 2,6-diisopropylaniline, 9.88 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.96 g (105 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After distilling off the solvent under reduced pressure, 90 ml of 2N hydrochloric acid was added. Neutralization with 10% aqueous potassium hydroxide and filtration gave a solid. The obtained solid was washed with water and then dried under reduced pressure to obtain a cream powder. Yield 11.21 g. In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand E

Under a nitrogen atmosphere, in a 50 ml Gildar flask, 30.8 mg (0.0336 mmol) of tris (benzylideneacetone) dipalladium, 20.7 mg (0.102 mmol) of tritert-butylphosphine, 0.655 g (2.26 mmol) of pyridine derivative E Then, 0.716 g of boronic acid derivative B, 20.1 g of THF, and 1.34 g of 5N aqueous sodium hydroxide solution were charged, and the mixture was stirred under reflux for 18 hours. 150 ml of hexane was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. After washing with methanol, the desired product was obtained by drying under reduced pressure. Yield 0.561 g, yield 52%. They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.00 (2H, dt, J = 8.8, 2.1 Hz), 7.83 (1H, t, J = 7.7 Hz), 7.72 ( 1H, dd, J = 7.9, 1.0 Hz), 7.49-7.21 (7H, m), 7.02-7.01 (3H, m), 4.13-4.11 ( 2H, br m), 3.89 (1H, br s), 3.15 (2H, sept, J = 7.0 Hz), 1.33 (9H, s), 1.02 (12H, d, J = 6.9 Hz).
FD-MS m / z = 476.3 (M +)

  (4) Synthesis of transition metal compound E

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.280 g (0.585 mmol) of ligand E, 0.189 g (0.589 mmol) of hafnium tetrachloride and 18.3 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 0.82 ml, 2.5 mmol) was added over 10 minutes. The mixture was stirred for 17 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was dissolved again in toluene, and insoluble matters were removed by filtration. The obtained solution was concentrated, washed with hexane, and then dried under reduced pressure to obtain the desired product. Yield 0.312 g, yield 78%. They were identified by ¹ H-NMR and single crystal X-ray structural analysis. The crystal used for the single crystal X-ray structure analysis was obtained by recrystallization using hexane.
¹ H-NMR (Toluene-d ₈ ) δ: 8.31 (1H, d, J = 2.3 Hz), 7.75 (1H, dd, J = 7.9, 1.0 Hz), 7. 67 (1H, d, J = 8.2 Hz), 7.44 (1H, dd, J = 8.4, 0.8 Hz), 7.32-7.17 (4H, m), 7.10 -6.89 (4H, m), 6.80 (1H, dd, J = 7.6, 1.0 Hz), 4.42-4.26 (2H, m), 4.01 (1H, d , J = 11.2 Hz), 2.85 (1H, ttt, J = 6.9, 6.9, 6.9 Hz), 1.53-1.47 (6H, m), 1.22 ( 9H, s), 0.81 (3H, d, J = 6.9 Hz), 0.66 (3H, s), 0.42 (3H, d, J = 6.6 Hz), − .29 (3H, s). (See Figure 5)

[Example 1F] Synthesis of transition metal compound F (1) Synthesis of pyridine derivative D

Under a nitrogen atmosphere, bis (diphenylphosphino) ferrocene 0.360 g (0.649 mmol), palladium acetate 0.145 g (0.648 mmol), biphenylboronic acid 2.57 g (13.0 mmol), , 6-dibromopyridine (3.69 g, 15.6 mmol), potassium hydroxide (0.874 g, 15.6 mmol) and acetonitrile (40.7 g) were charged, and the mixture was stirred under reflux for 18 hours. 50 ml of water was added and the solid was removed by filtration. Toluene was added to this solid and filtered. The resulting solution was concentrated and methanol was added. The precipitated solid was removed by filtration, washed with methanol, and dried under reduced pressure to obtain the desired product. Yield 1.90 g. In addition to the compound represented by the above formula, it was suggested that it contained impurities, but it was used in the next reaction as it was.

  (2) Synthesis of boronic acid derivative F

In a 100 ml eggplant flask equipped with a fractionator under a nitrogen atmosphere, 2.58 g (17.2 mmol) of 2-formylphenylboronic acid, 2.51 g (20.7 mmol) of 2,6-diisopropylaniline, 5.01 g of toluene, ethanol 35.6 g was charged. The mixture was stirred for 21 hours while distilling off the solvent under reflux. After adding 50 ml of methanol, 1.84 g (48.6 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After the solvent was distilled off under reduced pressure, 30 ml of 2N hydrochloric acid was added. Neutralized with 10% aqueous sodium hydroxide and filtered to obtain a solid. The obtained solid was washed with water and hexane and then dried under reduced pressure to obtain 1.97 g of a white powder.
Although it was suggested to be a mixture of a plurality of compounds, it was used in the next reaction as it was.

  (3) Synthesis of ligand F

In a 50 ml Gildar flask under nitrogen atmosphere, 35.7 mg (0.0390 mmol) of tris (benzylideneacetone) dipalladium, 20.1 mg (0.0994 mmol) of tri-t-butylphosphine, and the pyridine derivative D 0 obtained in (1). .801 g, 0.612 g of the boronic acid derivative F obtained in (2), 20.4 g of THF, and 1.22 g of 5N aqueous sodium hydroxide solution were charged, and the mixture was stirred for 20 hours under reflux. 150 ml of toluene was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. After washing with methanol, ethanol and hexane, the desired product was obtained by drying under reduced pressure. Yield 0.841 g, yield 35% (based on biphenylboronic acid). They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.13 (2H, dt, J = 8.6, 2.0 Hz), 7.84 (1H, t, J = 7.7 Hz), 7.77- 7.62 (6H, m), 7.51-7.27 (7H, m), 7.19 (1H, dd, J = 7.6, 1.6 Hz), 6.91 (2H, d, J = 7.6 Hz), 6.77 (1H, dd, J = 8.1, 6.8 Hz), 4.23 (2H, d, J = 6.3 Hz), 4.04 (1H, t, J = 6.4 Hz), 2.08 (6H, s).
FD-MS m / z = 440.2 (M +)

  (4) Synthesis of transition metal compound F

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.400 g (0.909 mmol) of the ligand F obtained in (3), 0.291 g (0.908 mmol) of hafnium tetrachloride and 18.0 g of toluene. Under an ice / acetone bath, an ether solution of methylmagnesium bromide (3.0 M, 1.25 ml, 3.75 mmol) was added over 10 minutes. The mixture was stirred for 16 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was dissolved again in toluene, and insoluble matters were removed by filtration. The obtained solution was concentrated, hexane was added, and unnecessary substances were removed by filtration. The resulting solution was concentrated and recrystallized at -20 ° C. The precipitated solid was removed by filtration and dried under reduced pressure to obtain the desired product. Yield 0.478 g, yield 81%.
They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 8.54 (1H, d, J = 1.6 Hz), 7.73 (1H, d, J = 7.9 Hz), 7.53-7. 40 (5H, m), 7.24-6.970 (8H, m), 6.88-6.73 (3H, m), 4.37 (1H, d, J = 11.5 Hz), 3 .77 (1H, d, J = 11.5 Hz), 2.71 (3H, s), 1.76 (3H, s), 0.64 (3H, s), −0.26 (3H, s (See Fig. 6)

[Example 1G] Synthesis of transition metal compound G (1) Synthesis of pyridine derivative G

Under a nitrogen atmosphere, 0.0845 g (0.073 mmol) of tetrakis (triphenylphosphine) palladium, 2.40 g (17.2 mmol) of p-fluorophenylboronic acid, 3.39 g of 2,6-dibromopyridine in a 100 ml three-necked flask ( 14.3 mmol), 1.97 g (18.6 mmol) of sodium carbonate, and 40 ml of ethanol were charged, followed by stirring under reflux for 18 hours. 50 ml of water was added and extracted with 150 ml of hexane. The organic layer was washed with water and a saturated aqueous sodium chloride solution and then dried over magnesium sulfate. After filtration, the solution was concentrated and the desired product was obtained by distillation under reduced pressure. Yield 1.09g. In addition to the compound represented by the above formula, it was suggested that it contained impurities, but it was used in the next reaction as it was.

  (2) Synthesis of ligand G

In a 50 ml Gildar flask under a nitrogen atmosphere, 68.8 mg (0.0751 mmol) of tris (benzylideneacetone) dipalladium, 48.0 mg (0.237 mmol) of tri-t-butylphosphine, and the pyridine derivative G 0 obtained in (1). 9469 g, 0.938 g of the boronic acid derivative B obtained in Example 01D (2), 20.0 g of THF, 1.89 g of 5N aqueous sodium hydroxide solution were charged, and the mixture was stirred for 18 hours under reflux. 100 ml of toluene was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. After purification by silica gel column chromatography, the mixture was heated to 220 ° C. under reduced pressure to remove volatile components. FD-MS analysis suggested that it was a mixture containing the desired product, but it was used in the next reaction as it was. Yield 1.06g.
FD-MS m / z = 438.3 (M +)

  (3) Synthesis of transition metal compound G

Under a nitrogen atmosphere, 0.408 g of the ligand G synthesized in (2), 0.288 g (0.900 mmol) of hafnium tetrachloride and 18.3 g of toluene were charged into a 30 ml Schlenk tube. Under an ice / acetone bath, an ether solution of methylmagnesium bromide (3.0 M, 1.25 ml, 3.75 mmol) was added over 10 minutes. The mixture was stirred for 22 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was dissolved again in toluene, and insoluble matters were removed by filtration. The resulting solution was concentrated and pentane was added. The precipitated solid was removed by filtration and dried under reduced pressure to obtain the desired product. Yield 0.440 g, yield 81%.
They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 7.96 (1H, dd, J = 7.9, 2.6 Hz), 7.72 (1H, dd, J = 7.7, 0.6 Hz) ), 7.47 (1H, dd, J = 8.6, 4.6 Hz), 7.28-7.14 (4H, m), 7.12-7.01 (2H, m), 6. 95 (1H, dd, J = 7.6, 1.6 Hz), 6.87 (1H, dd, J = 7.6, 1.6 Hz), 6.83-6.75 (2H, m) , 4.34-4.19 (2H, m), 3.99 (1H, d, J = 11.2 Hz), 2.65 (1H, sept, J = 6.9 Hz), 1.46 ( 6H, t, J = 6.8 Hz), 0.76 (3H, d, J = 6.9 Hz), 0.55 (3H, s), 0.42 (3H, d, J = 6.6) Hz), −0.34 (3H, s) (see FIG. 7).

[Example 1H] Synthesis of transition metal compound H (1) Synthesis of pyridine derivative H

Under a nitrogen atmosphere, bis (diphenylphosphino) ferrocene 0.230 g (0.415 mmol), palladium acetate 0.0928 g (0.413 mmol), p-methoxyphenylboronic acid 2.50 g (16.5 mmol) in a 100 ml three-necked flask ), 2,68-dibromopyridine (4.68 g, 19.8 mmol), potassium hydroxide (1.25 g, 22.2 mmol) and acetonitrile (39.9 g) were charged and stirred under reflux for 19 hours. Toluene (250 ml) was added, and the mixture was washed with water and a saturated aqueous sodium chloride solution. Dried over magnesium sulfate and concentrated the solution. Methanol was added, and the precipitated solid was removed by filtration, washed with toluene, and dried under reduced pressure to obtain the desired product. Yield 1.54g. Yield 35%
Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.95 (2H, dt, J = 9.5, 2.6 Hz), 7.62-7.51 (2H, m), 7.34 (1H, dt , J = 7.6, 0.7 Hz), 6.98 (2H, dt, J = 9.5, 2.6 Hz), 3.86 (3H, s).

  (2) Synthesis of ligand H

In a 50 ml Gildar flask under nitrogen atmosphere, 41.5 mg (0.0456 mmol) of tris (benzylideneacetone) dipalladium, 27.7 mg (0.137 mmol) of tri-t-butylphosphine, and the pyridine derivative H 0 obtained in (1). 804 g (3.04 mmol), 3.03 g of boronic acid derivative B obtained in Example 01D (2), 20.1 g of THF, 1.51 g of 5N aqueous sodium hydroxide solution were charged, and the mixture was stirred under reflux for 24 hours. did. 150 ml of toluene was added, and the organic layer was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. The desired product was obtained by purification by silica gel column chromatography. Yield 1.13 g, 82% yield.
They were identified by 1 H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ ) δ: 8.02 (2H, dt, J = 9.3, 2.5 Hz), 7.81 (1H, t, J = 7.7 Hz), 7.68 ( 1H, dd, J = 8.1, 0.8 Hz), 7.47 (1H, dd, J = 7.3, 1.6 Hz), 7.38-7.22 (4H, m), 7 .02-7.01 (3H, m), 6.94 (2H, dt, J = 9.6, 2.6 Hz), 4.13 (2H, s), 3.83 (4H, s + br s), 3.12 (2H, sept, J = 6.9 Hz), 1.02 (12H, d, J = 6.9 Hz).
FD-MS m / z = 450.3 (M +)

  (3) Synthesis of transition metal compound H

Under a nitrogen atmosphere, 0.400 g (0.888 mmol) of ligand H synthesized in (2), 0.285 g (0.891 mmol) of hafnium tetrachloride and 18.0 g of toluene were charged into a 30 ml Schlenk tube. Under an ice / acetone bath, an ether solution of methylmagnesium bromide (3.0 M, 1.25 ml, 3.75 mmol) was added over 10 minutes. The mixture was stirred for 17 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble matter was removed by filtration and concentrated. The precipitated solid was dissolved again in toluene, and insoluble matters were removed by filtration. The obtained solution was concentrated, pentane was added, and the precipitated solid was removed by filtration and dried under reduced pressure to obtain the desired product. Yield 0.495 g, yield 85%.
They were identified by ¹ H-NMR and single crystal X-ray structural analysis. Crystals used for single crystal X-ray structural analysis were obtained by recrystallization using toluene.
¹ H-NMR (Toluene-d ₈ ) δ: 7.77-7.74 (2H, m), 7.61 (1H, d, J = 8.6 Hz), 7.32-7.26 (2H m), 7.24-7.15 (2H, m), 7.11-6.97 (3H, m), 6.90 (1H, dd, J = 7.9, 1.6 Hz), 6.82 (1H, dd, J = 8.6, 3.0 Hz), 6.76 (1H, dd, J = 7.3, 1.0 Hz), 4.42-4.26 (2H, m), 4.03 (1H, d, J = 11.2 Hz), 3.32 (3H, s), 2.80 (1H, sept, J = 6.9 Hz), 1.52 (3H, d, J = 6.9 Hz), 1.47 (3H, d, J = 6.9 Hz), 0.81 (3H, d, J = 6.9 Hz), 0.62 (3H, s) , 0.50 (3H, d, J = 6.9 Hz), −0. 9 (3H, s). (See Figure 8)

[Example 1I] Synthesis of transition metal compound I (1) Synthesis of pyridine derivative A

Under a nitrogen atmosphere, bis (diphenylphosphino) ferrocene palladium dichloride 0.528 g (0.722 mmol), phenylboronic acid 1.93 g (15.8 mmol), 2,6-dibromopyridine 5.00 g (21) 0.1 mmol), 2.67 g (47.5 mmol) of potassium hydroxide, and about 50 ml of acetonitrile were charged, followed by stirring under reflux for 18 hours. Toluene (250 ml) was added, and the mixture was washed with water and a saturated aqueous sodium chloride solution. Dried over magnesium sulfate and concentrated the solution. Distillation under reduced pressure gave 1.98 g of a white solid. Of these, 1.41 g was recrystallized from methanol to obtain the desired product. Yield 0.492g. Yield 18.6%
(2) 6-bromo-1,1,4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene

Under a nitrogen atmosphere, in a 300 ml four-necked flask, 10.0 g (58.5 mmol) of 2,5-dichloro-2,5-dimethylhexane, 18.6 g (101 mmol) of o-bromotoluene, 100 ml of hexane, 0.0987 g of aluminum chloride (0.740 mmol) was charged. Stir for 2 hours under reflux. 0.303 g (2.27 mmol) of aluminum chloride was added, and the mixture was stirred for 1 hour under reflux. Further, 0.504 g (3.78 mmol) of aluminum chloride was charged and stirred for 19 hours under reflux. After adding 150 ml of hexane, it was washed twice with water and once with a saturated aqueous sodium chloride solution. The extract was dried over magnesium sulfate and concentrated. The obtained solid was washed with methanol and then dried under reduced pressure to obtain 11.2 g of the desired product. Yield 52%.
Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.42 (1H, s), 7.14 (1H, s), 2.34 (3H, s), 1.65 (4H, s), 1.25 ( 12H, s).

  (3) 6-bromo-7- (bromomethyl) -1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene

6-Bromo-1,1,4,4,7-pentamethyl-1,2,3,4-tetrahydronaphthalene 3.54 g (12.6 mmol) synthesized in (2) in a 100 ml four-necked flask under nitrogen atmosphere , Bromosuccinimide 2.70 g (102 mmol), carbon tetrachloride 50 ml, aluminum chloride 0.0987 g (0.740 mmol) were charged. A separately prepared Schlenk tube was charged with 1.57 g (4.83 mmol) of benzoyl peroxide (75 wt%, wet product) and about 10 ml of carbon tetrachloride. After stirring, the carbon tetrachloride phase was removed by decantation. Was added to the four-necked flask prepared. Stir for 4 hours under reflux. A carbon tetrachloride solution of 0.773 g (2.37 mmol) of benzoyl peroxide (75 wt%, wet product) prepared in the same manner was added and stirred for 4 hours under reflux. A carbon tetrachloride solution of 0.413 g (1.27 mmol) of benzoyl peroxide (75 wt%, wet product) prepared in the same manner and 0.713 g (4.01 mmol) of bromosuccinimide were added and stirred for 20 hours under reflux. did. After adding 100 ml of hexane, insoluble matters were removed by filtration. The filtrate was concentrated and purified by silica gel column chromatography to obtain 2.90 g of the desired product. Yield 64%
Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.45 (1H, s), 7.36 (1H, s), 4.57 (2H, s), 1.66 (4H, s), 1.26 ( 6H, s), 1.26 (6H, s).

  (4) N-((3-Bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl) methyl) -2,6-diisopropylaniline

Under a nitrogen atmosphere, 1.59 g (8.97 mmol) of 2,6-diisopropylaniline and 20.5 g of THF were charged into a 50 ml Gildar flask. An n-butyllithium / hexane solution (1.60 M, 5.3 ml, 8.5 mmol) was added dropwise over 20 minutes in a dry ice / acetone bath. The mixture was stirred for 3.5 hours while slowly returning to room temperature. 6.99 g (8.27 mmol) of 6-bromo-7- (bromomethyl) -1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene synthesized in (3) in a three-necked flask of 100 ml About 25 ml of THF was inserted. The previously prepared lithium-2,6-diisopropylanilide solution was added over 40 minutes in a dry ice / acetone bath. The mixture was stirred for 18 hours while returning to room temperature. After adding 300 ml of hexane, it was washed with water three times. After drying with magnesium sulfate, the solution was concentrated. Methanol was added, and the precipitated solid was removed by filtration and dried under reduced pressure to obtain 3.25 g of the desired product. Yield 86%
Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.46 (1H, s), 7.15 (1H, s), 7.10-7.01 (3H, m), 4.08 (2H, d, J = 7.3 Hz), 3.48 (1H, t, J = 7.3 Hz), 3.24 (2H, sept, J = 6.8 Hz), 1.64 (4H, s), 1. 26 (6H, s), 1.18 (12H, d, J = 6.8 Hz), 1.14 (6H, s).

(5) 2,6-diisopropyl-N-((5,5,8,8-tetramethyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5,6,7,8-tetrahydronaphthalen-2-yl) methyl) aniline

N-((3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl) methyl synthesized in (4) in a 50 ml Gildar flask under a nitrogen atmosphere ) -2,6-diisopropylaniline 1.00 g (2.21 mmol), bispinacolate diboron 0.840 g (3.31 mmol), potassium acetate 0.6483 g (6.61 mmol), bis (diphenylphosphino) ferrocene palladium 0.481 g (0.657 mmol) of dichloride and about 20 ml of dimethyl sulfoxide were charged. The mixture was stirred at 80 ° C. for 93 hours. After adding 200 ml of toluene, it was washed three times with water and once with a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, purification by silica gel column chromatography gave 0.510 g of the desired product. Yield 46%
Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.79 (1H, s), 7.05-6.95 (4H, m), 4.18 (2H, d, J = 7.9 Hz), 98 (1H, t, J = 7.9 Hz), 3.31 (2H, sept, J = 6.9 Hz), 1.64-1.59 (4H, m), 1.36 (12H, s ), 1.28 (6H, s), 1.15 (12H, d, J = 6.9 Hz), 1.08 (6H, s)

  (6) Synthesis of ligand I

Under a nitrogen atmosphere, 2,6-diisopropyl-N-((5,5,8,8-tetramethyl-3- (4,4,5,5-tetramethyl-) synthesized in (5) was added to a 50 ml Gildar flask. 1,3,2-dioxaborolan-2-yl) -5,6,7,8-tetrahydronaphthalen-2-yl) methyl) aniline 0.506 g (1.00 mmol), 2-bromo- synthesized from (1) 5-phenylpyridine 0.235 g (1.00 mmol), trisbenzylideneacetone dipalladium 0.0230 g (0.0251 mmol), tri-t-butylphosphine 0.0155 g (0.0766 mmol), 5N aqueous sodium hydroxide solution 0.605 g, THF About 25 ml was charged and stirred at 80 ° C. for 19 hours. After adding 150 ml of toluene, it was washed three times with water and once with a saturated aqueous sodium chloride solution. The extract was dried over magnesium sulfate and concentrated. Hexane was added and the precipitated solid was removed by filtration and washed with methanol to obtain 0.428 g of the desired product. Yield 80%
They were identified by ¹ H-NMR and FD-MS.
¹ H-NMR (Toluene-d ₈ ) δ: 8.21-8.15 (1H, m), 7.86 (1H, s), 7.68-7.62 (1H, m), 7.38 (1H, dd, J = 8.2, 0.7 Hz), 7.24-7.15 (4H, m), 7.13-6.89 (4H, m), 4.42 (1H, sept , J = 6.6 Hz), 4.30 (1H, d, J = 11.2 Hz), 4.04 (1H, d, J = 11.2 Hz), 2.83 (1H, sept, J = 6.6 Hz), 1.67-1.57 (10H, m), 1.45 (3H, s), 1.33 (3H, s), 1.29 (3H, s), 1.15. (3H, s), 0.82 (3H, d, J = 6.6 Hz), 0.59 (3H, s), 0.43 (3H, d, J = 6.6 Hz), -0.41 (3H, s).
FD-MS m / Z = 530.4

  (7) Synthesis of transition metal compound I

Under a nitrogen atmosphere, 0.416 g (0.783 mmol) of the ligand compound I synthesized in (6), 0.251 g (0.784 mmol) of hafnium tetrachloride, and about 20 ml of toluene were charged into a 30 ml Schlenk tube. Under an ice / acetone bath, an ether solution of methylmagnesium bromide (3.0 M, 1.20 ml, 3.6 mmol) was added over 10 minutes. The mixture was stirred for 17 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 30 ml of toluene. The insoluble material was removed by filtration and concentrated. The precipitated solid was dissolved again in toluene, and insoluble matters were removed by filtration. The obtained solution was concentrated, hexane was added, and the precipitated solid was removed by filtration and dried under reduced pressure to obtain the desired product. Yield 0.413 g, yield 71%.
Identified by ¹ H-NMR.
¹ H-NMR (Toluene-d ₈ ) δ: 8.21-8.15 (1H, m), 7.86 (1H, s), 7.68-7.62 (1H, m), 7.38 (1H, dd, J = 8.2, 0.7 Hz), 7.24-7.151 (4H, m), 7.13-6.89 (4H, m), 4.42 (1H, sept , J = 6.6 Hz), 4.30 (1H, d, J = 11.2 Hz), 4.04 (1H, d, J = 11.2 Hz), 2.83 (1H, sept, J = 6.6 Hz), 1.67-1.57 (10H, m), 1.45 (3H, s), 1.33 (3H, s), 1.29 (3H, s), 1.15 (3H, s), 0.82 (3H, d, J = 6.6 Hz), 0.59 (3H, s), 0.43 (3H, d, J = 6.6 Hz), −0. 41 (3H, s).

  [Synthesis Example 1a] Synthesis of transition metal compound a

Organometallics 2011, 30, 3318-3329 were synthesized by reference.

[Synthesis Example 1b] Synthesis of transition metal compound b (1) Synthesis of pyridine derivative b

Under a nitrogen atmosphere, a 100 ml three-necked flask was charged with 2.50 g (9.29 mmol) of 1-bromo-3,5-di-tert-butylbenzene and 50 ml of THF. Under cooling in a dry ice / acetone bath, n-butyllithium / hexane (1.60 M, 6.4 ml, 10 mmol) was added dropwise over 13 minutes. After 30 minutes, 1.18 g (11.3 mmol) of trimethoxyboron was charged. The mixture was stirred for 4 hours while gradually returning to room temperature. The solvent was distilled off under reduced pressure. Here, 2.18 g (9.18 mmol) of 2,6-dibromopyridine, 0.329 g (1.26 mmol) of triphenylphosphine, 0.094 g (0.42 mmol) of palladium acetate, 6.51 g of 5N aqueous sodium hydroxide solution, THF20 0.1 g was inserted and stirred under reflux for 17 hours. 150 ml of hexane was added, and the organic phase was washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solution was concentrated. The title compound was obtained by purifying by column chromatography and washing the resulting compound with methanol. Yield 0.618 g, yield 19%. Identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ) δ: 7.77 (2H, d, J = 1.8 Hz), 7.65 (1H, dd, J = 7.6, 1.0 Hz), 7.57 ( 1H, t, J = 7.7 Hz), 7.51 (1H, t, J = 1.8 Hz), 7.39 (1H, dd, J = 7.6, 1.0 Hz), 36 (18H, d, J = 10.2 Hz).

  (2) Synthesis of boronic acid derivative B

In a 200 ml eggplant flask equipped with a fractionator under a nitrogen atmosphere, 5.30 g (35.3 mmol) of 2-formylphenylboronic acid, 7.47 g (42.2 mmol) of 2,6-diisopropylaniline, 9.88 g of toluene, ethanol 100 ml was charged. The mixture was stirred for 20 hours while distilling off the solvent under reflux. After adding 100 ml of methanol, 3.96 g (105 mmol) of sodium borohydride was added in several portions in an ice water bath. It returned to room temperature and stirred for 2 hours. After distilling off the solvent under reduced pressure, 90 ml of 2N hydrochloric acid was added. Neutralization with 10% aqueous potassium hydroxide and filtration gave a solid. The obtained solid was washed with water and then dried under reduced pressure to obtain a cream powder. Yield 11.21 g. In addition to the compound represented by the above formula, it was suggested to be a mixture of a plurality of compounds such as methyl ester and dimer (dehydration condensate), but it was used in the next reaction as it was.

  (3) Synthesis of ligand b

Under a nitrogen atmosphere, 18.7 mg (0.0202 mmol) of tris (benzylideneacetone) dipalladium, 11.1 mg (0.0549 mmol) of tritert-butylphosphine, (pyridine derivative b0.2834 g, boronic acid derivative b0 .283 g, THF 20.0 g, 5N aqueous sodium hydroxide solution 0.537 g were added and stirred under reflux for 16 hours, 150 ml of hexane was added, and the organic layer was washed with water and saturated aqueous sodium chloride solution and dried over magnesium sulfate. Thereafter, the solvent was distilled off, and the product was obtained by purification by silica gel column chromatography, yield 0.4211 g.
¹ H-NMR and FD-MS suggested a small amount of impurities, but they were used in the next reaction as they were.
FD-MS m / z = 532.4 (M +)

  (4) Synthesis of transition metal compound b

Under a nitrogen atmosphere, a 30 ml Schlenk tube was charged with 0.398 g of the ligand b obtained in (3), 0.242 g (0.755 mmol) of hafnium tetrachloride, and 19.18 g of toluene. Under an ice / acetone bath, methyl magnesium bromide in diethyl ether (3.0 M, 1.0 ml, 3.1 mmol) was added over 10 minutes. The mixture was stirred for 21 hours while slowly returning to room temperature. The solvent was distilled off, and the soluble component was extracted with 20 ml of hexane. The insoluble matter was removed by filtration and concentrated. It was dissolved again in 5 ml of hexane, and insoluble matters were removed by filtration. The obtained solution was concentrated, hexane was added, and unnecessary substances were removed by filtration. The obtained solution was concentrated and recrystallized at −20 ° C. using pentane. The precipitated solid was removed by filtration, and the resulting solution was concentrated and recrystallized again with pentane. The precipitated solid was removed by filtration and dried under reduced pressure to obtain the desired product. Yield 65.8 mg.
They were identified by ¹ H-NMR and X-ray crystal structure analysis.
¹ H-NMR (Toluene-d ₈ ) δ: 8.01 (2H, d, J = 2.0 Hz), 7.88 (1H, dd, J = 7.4, 1.2 Hz), 7. 56 (1H, t, J = 1.8 Hz), 7.46 (1H, dd, J = 7.9, 1.0 Hz), 7.31-6.94 (8H, m), 4.91 (2H, s), 3.48 (2H, sept, J = 6.9 Hz), 1.33 (18H, s), 1.16 (6H, d, J = 6.9 Hz), 1.00 (6H, d, J = 6.6 Hz), 0.092 (9H, s). (See Figure 9)

  [Synthesis Example 1c] Synthesis of transition metal compound c

A zirconium compound was synthesized using hafnium tetrachloride with reference to a synthesis example of a zirconium compound disclosed in Japanese Patent Application Laid-Open No. 2004-16874.

  [Synthesis Example 1d] Synthesis of Transition Metal Compound d

A zirconium compound was synthesized using hafnium tetrachloride with reference to a synthesis example of a zirconium compound disclosed in Japanese Patent Application Laid-Open No. 2004-16874.

[Examples 2A to 2L] Ethylene Polymerization 250 ml of a solvent was placed in a gas-flowing glass polymerizer having an internal volume of 500 ml that was sufficiently purged with nitrogen. Ethylene was passed at 150 liters / hour at the polymerization temperature and normal pressure shown in Table 1 to fully saturate the system. The aluminum compound was then added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. The system was polymerized while maintaining the polymerization temperature described in Table 1. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The resulting polymerization solution was treated as follows depending on the type of solvent used.

  When toluene was used: It was added to 2 L of methanol containing 1 ml of concentrated hydrochloric acid and stirred sufficiently. The precipitated polymer was taken out by filtration, washed with methanol, and dried at 80 ° C. for 10 hours under reduced pressure.

  When n-decane was used: The polymerization solution was placed in a mixed solvent (concentrated hydrochloric acid 1 ml / methanol 700 ml / acetone 800 ml) (sufficiently stirred and filtered. The polymer was washed with a large amount of methanol. The polymerization conditions and results are summarized in Table 1. The amount of unsaturated bonds was determined by Method B).

[Comparative Examples 2A and 2B] Ethylene polymerization The same procedure as in Example 2A was performed. The polymerization conditions and results are summarized in Table 1.

[Examples 3A to 3K] Propylene Polymerization Into a gas-flowing glass polymerizer with an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was placed, and propylene was circulated at 50 liters and normal pressure at 150 liters / hour. The system was fully saturated. The aluminum compound was then added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. Polymerization was carried out while maintaining the system at 50 ° C. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The polymerization solution was treated by any of the following methods a), b) and c) according to the properties of the obtained polymer, and then dried at 80 ° C. for 10 hours under reduced pressure. The polymerization conditions and results are summarized in Table 2. The amount of unsaturated bonds was determined by method A).

Processing a)
The obtained polymerization solution was added to 2 L of methanol containing 1 ml of concentrated hydrochloric acid and sufficiently stirred. The precipitated polymer was removed by filtration and washed with methanol.

Processing b)
The obtained polymerization solution was washed with 1N hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over magnesium sulfate. The desiccant was filtered off and concentrated under reduced pressure.

Process c)
After adding a small amount of toluene to the polymer obtained by the process b), the polymer was separated by the process a).

[Comparative Examples 3A, 3B] Propylene polymerization The same procedure as in Example 3A was performed. The polymerization conditions and results are summarized in Table 2.

[Examples 4A to 4H] Ethylene / propylene copolymer 250 ml of toluene was placed in a gas-flowing glass polymerizer with an internal volume of 500 ml sufficiently purged with nitrogen, and a mixed gas (volume) of ethylene and propylene at 50 ° C and normal pressure. The ratio 1: 1) was passed at 150 liters / hour to fully saturate the system. The aluminum compound was then added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. Polymerization was carried out while maintaining the system at 50 ° C. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The polymerization solution was treated by any of the methods a), b) and c) of [Examples 3A to F] according to the properties of the obtained polymer, and then dried at 80 ° C. for 10 hours under reduced pressure. The amount of unsaturated bonds was determined by method A). The polymerization conditions and results are summarized in Table 3.

[Comparative Example 4A] Ethylene / propylene copolymerization The same procedure as in Example 4A was performed. The polymerization conditions and results are summarized in Table 3.

[Examples 5A to 5C] Ethylene / octene copolymerization A predetermined amount of n-decane (250 ml) and octene were placed in a gas-flowing glass polymerizer having an internal volume of 500 ml that had been sufficiently purged with nitrogen. Ethylene was passed at 150 liters / hour at 100 ° C. and normal pressure to fully saturate the system. The aluminum compound was then added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. Polymerization was carried out while maintaining the system at 100 ° C. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The obtained polymerization solution was put into a mixed solvent of 1 ml of concentrated hydrochloric acid / 700 ml of methanol / 800 ml of acetone, sufficiently stirred and filtered. The polymer was washed with a large amount of methanol and dried at 120 ° C. under reduced pressure for 10 hours. The polymerization conditions and results are summarized in Table 4.

[Comparative Example 5A] Ethylene / octene copolymerization The same procedure as in Example 5A was performed. The polymerization conditions and results are summarized in Table 4.

[Examples 6A to 6C] Ethylene / propylene / 5-ethylidene-2-norbornene copolymerization Into a gas-flowing glass polymerizer having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of n-decane and 5-ethylidene-2- A predetermined amount of norbornene was added, and a mixed gas of ethylene and propylene (volume ratio of 1: 1) was circulated at 100 ° C. and normal pressure at 150 liters / hour to fully saturate the system. The aluminum compound was then added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. Polymerization was carried out while maintaining the system at 100 ° C. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The obtained polymerization solution was put into a mixed solvent of 1 ml of concentrated hydrochloric acid / 700 ml of methanol / 800 ml of acetone, sufficiently stirred and filtered. The polymer was washed with a large amount of methanol and dried at 120 ° C. under reduced pressure for 10 hours. The polymerization conditions and results are summarized in Table 5.

Comparative Example 6A Ethylene / propylene / 5-ethylidene-2-norbornene copolymerization The same procedure as in Example 6A was performed. The polymerization conditions and results are summarized in Table 5.

[Example 7A] Ethylene / propylene block copolymer 250 ml of n-decane was placed in a gas-flowing glass polymerizer having an internal volume of 500 ml sufficiently purged with nitrogen, and ethylene was 150 liters / hour at 100 ° C. and normal pressure. In order to fully saturate the system. Next, 0.50 ml of a toluene solution of triisobutylaluminum (1 mol / l) was added. To this, 1.00 ml of a 2 mmol / l toluene solution of transition metal compound A and 0.80 ml of a 5 mmol / l toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added. The system was polymerized for 3 minutes while maintaining the system at 100 ° C. The supply of ethylene was stopped, and nitrogen gas was circulated at 150 liters / hour for 10 minutes. Nitrogen gas was stopped and propylene was circulated at 150 liters / hour. After 1 minute, 3.00 ml of a 2 mmol / l toluene solution of a transition metal compound (catalyst) and 0.80 ml of a 5 mmol / l toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added. The polymerization was stopped by adding a small amount of isobutyl alcohol and stopping the gas supply. The obtained polymerization solution was added to a mixed solvent of 700 ml of methanol containing 1 ml of concentrated hydrochloric acid and 800 ml of acetone, and sufficiently stirred. The precipitated polymer was taken out by filtration, washed with methanol, and dried at 120 ° C. for 10 hours under reduced pressure.

The obtained polymer was 4.16 g. As a result of DSC measurement, the melting point was 120.3 ° C. In addition, the propylene content is 15.4 mol%, the polypropylene (PP) partial stereoregularity (mm / mr / rr) is 16.9 / 48.2 / 34.9, the PP part heterogeneous bond (2,1-insertion) amount Was 2.9%. The amount of unsaturated bonds was determined by method B). ^The results of ¹³ C-NMR measurement are shown in FIG. Further, the content of terminal structure A, terminal structure B, and terminal structure C per 1000 carbon atoms determined by ¹³ C-NMR, and the amount of unsaturated bond of the polymer was determined by method B). Table 6 shows the content of terminal vinyl groups and terminal vinylidene groups per unit. Terminal structures A, B, and C are those shown in FIG. Furthermore, the TREF curve obtained from the CFC measurement is shown in FIG.

[Examples 8A to 8D] Ethylene / tetracyclododecene copolymerization Into a gas-flowing glass polymerizer having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of cyclohexane and 1,2,3,4,4a, 5,8 , 8a-octahydro-1,4: 5,8-dimethanonaphthalene (described as tetracyclododecene or TD) is added in a predetermined amount, and ethylene gas is circulated at 50 ° C. and normal pressure at 150 liters / hour, The system was fully saturated. Subsequently, the MMAO-3A solution (0.30 mmol as Al amount) was added. A toluene solution of a transition metal compound (catalyst) and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (2 equivalents relative to the transition metal compound) were added thereto. The system was polymerized for 10 minutes while maintaining the system at 50 ° C. The polymerization was stopped by adding a small amount of methanol and stopping the gas supply. The obtained polymerization solution was put into a mixed solvent of 1 ml of concentrated hydrochloric acid / 700 ml of methanol / 800 ml of acetone, sufficiently stirred and filtered. The polymer was washed with a large amount of methanol and dried at 120 ° C. under reduced pressure for 10 hours. The polymerization conditions and results are summarized in Table 7.

  The subject of this invention can provide the manufacturing method of the olefin polymerization catalyst which is excellent in catalyst activity, and gives a more useful olefin polymer, and the manufacturing method of an olefin polymer, and is industrially very valuable.

Claims (11)

The catalyst for olefin polymerization containing the transition metal compound (I) represented by the following general formula (I).
(In the general formula (I), Q ^{1 to} Q ⁵ each independently represents a carbon atom or a silicon atom, and a single bond between adjacent atoms of Q ^{1 to} Q ⁵ is replaced by a multiple bond. R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, or a phosphorus-containing group. , A silicon-containing group, a germanium-containing group, or a tin-containing group, and the hydrogen atom contained in the hydrocarbon group is a halogen atom, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, sulfur May be substituted by at least one substituent selected from a containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and two or more of these R ^{1 to} R ¹⁰ are connected to each other. Forming a ring The hydrogen atom contained in the ring may be a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group. When at least one substituent selected from a group, a germanium-containing group, and a tin-containing group may be substituted, and a single bond between adjacent atoms among Q ^{1 to} Q ⁵ is replaced with a multiple bond Is a part of R ^{1 to} R ¹⁰ depending on the valence of the multiple bond, T represents a nitrogen atom or a phosphorus atom, A represents a hydrocarbon group or a hetero element-containing hydrocarbon group. , X represents a C1-C30 cyclic hydrocarbon group containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, M represents a group 3-10 transition metal element in the periodic table, and X and M Dotted line between and indicates coordination bond , L represents a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can be coordinated by a lone pair, n is an integer of 1 to 4, and when n is 2 or more, L May be the same or different.) In the general formula ^{(I), Q 3 (R} 5 R 6) moieties represented by ^{-X-Q 4 (R 7 R} 8) is, according to claim 1 represented by the structure of the following general formula (II) Olefin polymerization catalyst.
(In the general formula (II), R ^{11 to} R ¹³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{11 to} R ¹³ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and Q ³ , Q ⁴ and R ^{5 to} R ⁸ is the same as defined in general formula (I).) In the above general formula (I), the moiety represented by XQ ⁴ (R ⁷ R ⁸ ) -Q ⁵ (R ⁹ R ¹⁰ ) -M is represented by the structure of the following general formula (III): 2. The olefin polymerization catalyst according to 2.
(In the general formula (III), R ^{14 to} R ¹⁷ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{14 to} R ¹⁷ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and X and M in the general formula (I) Same as definition.) In the above general formula (I), the moiety represented by XQ ³ (R ⁵ R ⁶ ) -Q ² (R ³ R ⁴ ) -Q ¹ (R ¹ R ² ) is a structure of the following general formula (IV) The catalyst for olefin polymerization of any one of Claims 1-3 shown by these.
(In the general formula (IV), R ^{18 to} R ²¹ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heteroelement-containing hydrocarbon group having 1 to 30 carbon atoms, Two or more of these R ^{18 to} R ²¹ may be connected to each other to form a ring, and the ring further includes a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It may have at least one substituent selected from a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and X, Q ¹ , R ¹ and R ² Is the same as defined in general formula (I).) The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein a moiety represented by TA in the general formula (I) is represented by a structure of the following formula (VII).
(In the formula (VII), R ²⁶ ~R ³⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, shows a hetero element-containing hydrocarbon group having 1 to 30 carbon atoms, these R ²⁶ ~ Two or more of R ³⁰ may be connected to each other to form a ring, and the hydrogen atom contained in the ring is further a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group And may be substituted with at least one substituent selected from a group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. The olefin polymerization catalyst according to claim 5, wherein in the general formula (VII), at least one selected from R ²⁶ and R ³⁰ is a hydrocarbon group having 1 to 30 carbon atoms.   The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein in the general formula (I), M is a Group 4 transition metal element in the periodic table.   The olefin polymerization catalyst according to claim 7, wherein M in the general formula (I) is hafnium. In addition to the transition metal compound (I),
(B-1) an organometallic compound,
It contains at least one compound (B) selected from (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with a transition metal compound (I) to form an ion pair. The catalyst for olefin polymerization of any one of -8. In addition to the (B-1) organometallic compound,
It contains at least one compound selected from (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with a transition metal compound (I) to form an ion pair. The catalyst for olefin polymerization described in 1.   An olefin polymer for 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 any one of claims 1 to 10. Production method.