JP2006347899A - Transition metal compound, method for producing transition metal compound, olefin polymerization catalyst component composed of transition metal compound and method for polymerizing olefin by using olefin polymerization catalyst component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transition metal compound having excellent olefin polymerization performance. <P>SOLUTION: The new transition metal compound (A) has a structure expressed by general formula (1). An example of the compound is [diphenylsilyl(octamethyloctahydrodibenzofluorenyl)(4,6-di-t-butylphenoxy)]titanyl dichloride. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel transition metal compound, a method for producing the transition metal compound with high yield, an olefin polymerization catalyst component comprising the transition metal compound, and an olefin polymerization method using the olefin polymerization catalyst. .

  As the olefin polymerization catalyst, a Kaminsky catalyst using a so-called cyclopentadienyl group as a ligand is well known. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of transition metal compounds used in such Kaminsky catalysts include bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Laid-Open No. 58-19309) and ethylene bis (4,5,6,7-tetrahydroindene). Nyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) and the like are known.

  It is also known that the olefin polymerization activity and the properties of the resulting polyolefin differ greatly when the transition metal compound used in the polymerization is different. Polyolefins have excellent mechanical properties and are used in various fields such as for various molded products. Recently, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. .

  Therefore, the appearance of a catalyst component for olefin polymerization excellent in the properties of the obtained polyolefin is desired, and the appearance of a new transition metal compound capable of becoming such a catalyst component for olefin polymerization is desired.

  Recently, many improvements have been made to a method for polymerizing olefins using a catalyst system containing a monocyclopentadienyl compound to which a group containing a heteroatom such as a nitrogen atom, an oxygen atom, or a phosphorus atom is bonded. Chem. Rev. 1998 (98), 2587 and Chem. Rev., 2003 (103), 2633, and the like.

  On the other hand, the present inventors have disclosed a catalyst system containing a novel transition metal compound exhibiting ethylene polymerization activity in JP-A-8-325283.

  Following the disclosure of the present inventors, as a similar phenolate transition metal compound, US5856258, Organometallics, 1997 (16), 5958, Organometallics, 2003 (22), 3877, and Organometallics, 2004 (23), 540, etc.

   In addition, as an analog of the above-described phenolate transition metal compound, a transition metal compound having a structure in which a phenoxy group and a monocyclopentadienyl group are bridged by an atom of Group 14 of the periodic table is described in J. Organometallic Chemistry, 1997 ( 547), 263, and JP-A-9-87313.

However, in the polymerization using the phenolate transition metal compound used in these prior arts, any catalyst still has a polymerization performance in the homopolymerization of ethylene or α-olefin and the copolymerization of ethylene and α-olefin. In view of the fact that the polymer is not sufficient and the stereoregularity of the obtained polymer is not sufficient in the homopolymerization of α-olefin, the appearance of a catalyst containing a novel transition metal compound having further excellent polymerization performance has been desired. .
JP 58-19309 A JP 61-130314 A JP-A-8-325283 US5856258 JP-A-9-87313 Chem. Rev., 1998 (98), 2587 Chem. Rev., 2003 (103), 2633 Organometallics, 1997 (16), 5958 Organometallics, 2003 (22), 3877 Organometallics, 2004 (23), 540 J. Organometallic Chemistry, 1997 (547), 263

In general, polyolefins are used in various fields such as for various molded products because they are excellent in mechanical properties. However, in recent years, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. Yes. However, the conventional catalyst as described above has not been sufficient in polymerization performance. That is, the problem to be solved by the present invention is to provide an olefin polymerization catalyst that is excellent in olefin polymerization performance and can produce a polyolefin having excellent properties.

  When the present inventors earnestly examined about the transition metal compound which has the novel structure which gives the olefin polymer which solved the said subject, and the polymerization method using the same, the specific formula represented by following General formula (1) is shown. The inventors have succeeded in developing a novel transition metal compound having a structure, and have found that the above-mentioned problems can be solved by polymerization using the transition metal compound (A). In other words, by using the transition metal compound (A) obtained in the present invention as a main catalyst, (co) polymerization of olefin proceeds with high polymerization activity, and in the homopolymerization of α-olefin, conventional non-crosslinking, Further, the present inventors have found that a polyolefin having a high stereoregularity as compared with a bridged phenolate-based transition metal compound and having a very high comonomer content in the copolymerization of olefins can be produced.

  That is, the first invention in the present invention is a novel transition metal compound (A) having a structure represented by the following general formula (1).

[In General Formula (1), M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and the atoms or groups represented by R ^{1 to} R ⁸ are a hydrogen atom, a halogen atom, a hydrocarbon group, A group selected from a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, which may be the same or different from each other, but R ³ and R ⁶ are not hydrogen at the same time, R ¹ Two groups adjacent to each other among the atoms or groups represented by ˜R ⁸ may be bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded; ^{9 to} R ¹² may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ^8, and two adjacent groups among the atoms or groups represented by R ^{9 to} R ¹² are Combine to form an aromatic, aliphatic, or heterocyclic ring with their attached carbon atoms It may be. Q represents a carbon atom, a silicon atom, boron, aluminum, gallium, indium, or thallium, and R ¹³ and R ¹⁴ may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ⁸ Two of the atoms or groups represented by R ¹³ and R ¹⁴ may be bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. Good. X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and D represents —O—, —S—, —NR ^a —, — PR ^b- represents, and R ^a and R ^b represent a hydrogen atom or a hydrocarbon group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are the same as each other However, they may be different, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a nonconjugated linear diene, or a nonconjugated branched diene. In addition, a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a nonconjugated cyclic diene, and n Represents an integer of 0 to 3. ]
The second invention in the present invention relates to an olefin polymerization catalyst comprising a novel transition metal compound represented by the general formula (1), and an olefin polymerization method using the olefin polymerization catalyst.

  The novel transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization, and can be used for polymerization of ethylene, propylene, butene, decene, butadiene, etc., and copolymerization of ethylene / propylene, ethylene / butene copolymer, etc. When performed, the polymerization proceeds with high polymerization activity. In addition, when ethylene homopolymerization is performed, an ethylene polymer having an alkyl side chain is obtained, and when homopolymerization of α-olefin such as propylene, butene, and decene is performed, conventional non-bridged and bridged phenolate transition A polymer having higher stereoregularity than a polymer obtained from a metal compound can be obtained. On the other hand, when copolymerization is performed, the copolymerization of the comonomer is extremely excellent, and a copolymer having a high comonomer content can be obtained when a small amount of comonomer is used, compared to conventional olefin polymerization catalysts. The branched olefins can be copolymerized and are extremely valuable industrially.

  Hereinafter, a novel transition metal compound according to the present invention, an olefin polymerization catalyst comprising the transition metal compound, and an olefin polymerization method using the same will be described in detail. In the present specification, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. Sometimes used in the inclusive sense.

  First, the novel transition metal compound (A) of the present invention will be described.

[Transition metal compound (A)]
The novel transition metal compound (A) of the present invention is represented by the following general formula (1).

  In the above general formula (1), M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, specifically, Group 4 metal atoms of titanium, zirconium, and hafnium, vanadium, niobium, and tantalum 5 of tantalum. Group 6 metal atom, chromium, molybdenum, tungsten group 6 metal atom. Of these, transition metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, and chromium are preferable. Among them, Group 4 metal atoms and Group 5 metal atoms are preferable, and the valence state of transition metal atom M Is more preferably a divalent, trivalent or tetravalent group 4 or 5 transition metal atom of the periodic table, particularly preferably titanium, zirconium, hafnium or vanadium.

R ^{1 to} R ⁸ represent a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and may be the same or different from each other good but, R ³ and R ⁶ are not simultaneously hydrogen, and preferably may not be group simultaneously hydrogen adjacent to, more preferably when R ³ and R ⁶ are not both hydrogen, among others R ^2, R ^3, It is particularly preferred that all of R ⁶ and R ⁷ are not hydrogen. Specific examples of R ^{1 to} R ⁸ include halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl , Alkenyl groups such as vinyl, allyl, isopropenyl, arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, A hydrocarbon group having 1 to 30 carbon atoms such as an aryl group such as phenanthryl; a halogenated hydrocarbon group having 1 to 30 carbon atoms in which a halogen atom is substituted for the hydrocarbon group having 1 to 30 carbon atoms; A silyl atom is placed on 1 to 30 hydrocarbon groups. The substituted C1-C30 silylated hydrocarbon group is mentioned.

Moreover, two groups adjacent to each other among the atoms or groups represented by R ^{1 to} R ⁸ are bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. Of these, it is preferable that at least one of R ² and R ³ , or R ⁶ and R ⁷ is bonded to form a ring, and specifically, as a fluorenyl group satisfying such requirements, Groups such as 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo [b] fluorenyl group, and R ² and R ³ , and R ⁶ and R ⁷ are simultaneously It is particularly preferable that they are bonded to form a ring, and among them, R ² and R ³ , and R ⁶ and R ⁷ are simultaneously bonded to form a 6-membered or higher aliphatic ring. Particularly preferred fluorenyl groups satisfying such requirements are specifically 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10 -octahydrobenzo [b, h] and groups such as a fluorenyl group.

R ^{9 to} R ¹² may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ^8, and two adjacent groups among the atoms or groups represented by R ^{9 to} R ¹² May combine to form an aromatic ring or an aliphatic ring such as benzene, naphthalene, acenaphthene and the like together with the carbon atoms to which they are bonded.

Among these, R ⁹ is preferably a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silylated hydrocarbon group having 1 to 20 carbon atoms, specifically, Alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl, arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, trityl, phenyl, tolyl, dimethylphenyl Hydrocarbon groups having 1 to 20 carbon atoms such as aryl groups such as trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; and the like. A halogenated hydrocarbon group having 1 to 20 carbon atoms; the carbon having 1 to 20 carbon atoms Silyl atom hydrogen group is silylated hydrocarbon group having 1 to 20 carbon atoms which is substituted.

In particular, it is more preferable that R ⁹ is a tertiary hydrocarbon group, a tertiary silylated hydrocarbon group, an aromatic substituted aliphatic group, an aromatic group or an alicyclic group, specifically, t-butyl, Alkyl groups such as norbornyl, adamantyl, arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, trityl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, etc. A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group of the above; a halogenated hydrocarbon group having 1 to 20 carbon atoms in which a halogen atom is substituted for the hydrocarbon group having 1 to 20 carbon atoms; the carbonization having 1 to 20 carbon atoms And a silylated hydrocarbon group having 1 to 20 carbon atoms in which a silyl atom is substituted on the hydrogen group, and more preferably a tert-butyl group. Hydrocarbon groups having 1 to 20 carbon atoms such as aryl groups such as adamantyl, trityl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; trimethylsilyl, methyldiphenyl Examples thereof include silylated hydrocarbon groups having 1 to 20 carbon atoms in which a silyl atom is substituted for the above hydrocarbon groups having 1 to 20 carbon atoms such as silyl, dimethylphenylsilyl, and triphenylsilyl.

 Q represents a carbon atom, a silicon atom, boron, aluminum, gallium, indium, or thallium, preferably a carbon atom, a silicon atom, or a boron atom, and particularly preferably a carbon atom or a silicon atom.

R ¹³ and R ¹⁴ may be the same or different from each other, and represent the same atom or group as R ^{1 to} R ^8, and two adjacent groups among the atoms or groups represented by R ¹³ and R ¹⁴ May be bonded together to form an aromatic ring, an aliphatic ring or a heterocycle together with the carbon atom to which they are bonded and Q, specifically, cyclopropylidene, cyclobutylidene, cyclopentyl Cycloaliphatic rings such as lidene, cyclohexylidene, cycloheptylidene, or cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, octoheptamethylenesilylene may be formed.
R ¹⁵ represents the same atom or group as R ^{1 to} R ⁸ .

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group, and D represents —O—, —S—, —NR ^a —, —PR ^b —. R ^a and R ^b represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are the same as each other However, they may be different, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a nonconjugated linear diene, or a nonconjugated branched diene. In addition, a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a nonconjugated cyclic diene, and n Represents an integer of 0 to 3.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl And aryl groups such as phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.

  Specific examples of the oxygen-containing group include an oxy group, a peroxy group, a hydroxy group, a hydroperoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.

  Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino Arylamino groups or alkylarylamino groups such as: methylimino, ethylimino group, i-propylimino group, t-butylimino group, etc .; alkylimino groups such as phenylimino, 2-methylphenylimino group, 2,6-dimethylphenylimino Group, 2,4,6-trimethylphenylimino group, 2-i-propylphenylimino group, 2,6-di-i-propylphenylimino group, 2,4,6-tri-i-propylphenylimino group, 2-t-butylphenylimino group, 2,6-di-t-butylphenylimino group, 2,4,6-tri-t-butyl Arylimino groups such as ruphenylimino groups; trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine ( alkyl or arylamine groups such as tppda).

  When X is an alkylimino group or an arylimino group, M and X are bonded by a double bond.

  When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

m is a number that satisfies the valence of M, is determined by the valence of the transition metal atom M and the valence of X, and is such a number that these positive and negative valences are neutralized. Here, when the absolute value of the valence of the transition metal atom M is a and the absolute value of the valence of X is b, the relationship a-2 = b × n is established. More specifically, for example, if M is Ti ⁴⁺ and X is Cl ⁻ , n is 2.

D represents —O—, —S—, —NR ^a —, or —PR ^b —, and is particularly preferably oxygen. R ^a and R ^b represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group include the same hydrocarbons having 1 to 20 carbon atoms as R ^{1 to} R ⁸ described above. Among these, a hydrocarbon group is preferable, and a hydrocarbon group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, benzyl, phenyl, tolyl, dimethylphenyl, and naphthyl is particularly preferable.

  In the general formula (1), Y represents a neutral ligand having an electron-donating group, and n representing the number of Y represents an integer of 0 to 3, preferably 1 or 2. The electron donating group is a group having an unpaired electron that can be donated to a metal, and Y may be any neutral ligand as long as it has an electron donating property. Specific examples of the neutral ligand Y include linear or cyclic chains such as diethyl ether, dimethyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, furan, dioxane, dimethylfuran, anisole, diphenyl ether, and methyl-t-butyl ether. Saturated or unsaturated ethers such as acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde, p-nitrobenzaldehyde, p-tolualdehyde, phenylacetaldehyde and the like linear or cyclic saturated or unsaturated aldehydes such as acetone, methyl ethyl ketone Linear or cyclic saturated or unsaturated ketones such as methyl-n-propyl ketone, acetophenone, benzophenone, n-butyrophenone, benzylmethyl ketone, such as formamide , Acetamide, benzamide, n-valeramide, stearylamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylpropionamide, N, N-dimethyl-n-butyramide, etc. Or unsaturated amides, for example, linear or cyclic saturated or unsaturated anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, for example linear or cyclic saturated or unsaturated imides such as succinimide, phthalimide, etc. Chain or cyclic saturated or unsaturated esters such as methyl acetate, ethyl acetate, benzyl acetate, phenyl acetate, ethyl formate, ethyl propionate, ethyl stearate, ethyl benzoate, such as trimethylamine, triethylamine, triphenylamine, dimethyl Amines, N, N, N ′, N′-tetramethylethylenediamine, Linear or cyclic saturated or unsaturated amines such as niline, N, N-dimethylaniline, pyrrolidine, piperidine, morpholine, such as pyridine, α-picoline, β-picoline, quinoline, isoquinoline, 2-methylpyridine, pyrrole, Nitrogen-containing heterocyclic compounds such as oxazole, imidazole, pyrazole, and indole, for example, sulfur-containing heterocyclic compounds such as thiophene and thiazole, such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, and triphenylphosphine Preserving phosphines, for example aceto, saturated or unsaturated nitriles such as tolyl, benzonitrile, inorganic salts such as lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, inorganics such as carbon monoxide and carbon dioxide Compounds such as Organometallic compounds is mentioned (B-1), and the like. Furthermore, a compound in which a part of these compounds is substituted with a substituent such as an alkyl group, a halogen group, a nitro group, a carbonyl group, or an amino group may be used. As Y in the formula (1), among these neutral ligands, ethers, aldehydes, ketones, nitrogen-containing heterocyclic compounds, and inorganic salts are preferable.

[Production Method of Transition Metal Compound (A)]
The transition metal compound (A) of the present invention is characterized by being produced by carrying out the following steps. That is, a neutral ligand (L1) having a structure represented by the following general formula (2), which is a precursor of the transition metal compound (A), is converted into a dianion ligand having a structure represented by the following general formula (3). (L2) is a method for producing a novel transition metal compound (A) by reacting a transition metal compound represented by the following general formula (4), which comprises a neutral ligand (L1 ) In the step of converting dianion (L2) into a dianion (L2), comprising the step of preparing a dianion ligand (L2) by reacting an organic alkali metal in the presence of an alkoxide having 3 or more carbon atoms It is a manufacturing method of a transition metal compound (A).

In the above general formula (2), general formula (3), and general formula (4), R ^{1 to} R ¹⁴ , M, Q, D, X, Y, and m and n are in the general formula (1). And R ¹⁵ is the same atom or group as R ^{1 to} R ⁸ .

  Hereafter, the manufacturing method of the transition metal compound (A) concerning this invention is explained in full detail. First, in the synthesis of the dianion ligand (L2) having the structure represented by the general formula (2), the neutral ligand (L1) having the structure represented by the general formula (2) is used. 1990 (46), 5633, Angew. Chem., Int. Ed. 1973 (12), 508, J. Organomet. Chem. 1967 (8), 9 or the like, or similar methods It can be obtained by carrying out the reaction. After completion of the reaction, if it is confirmed that the reaction is proceeding quantitatively by NMR or the like, it can be used for the next reaction as it is. The usual operation used when purifying the transition metal complex such as extraction and recrystallization is used. The solvent used for extraction and recrystallization is not particularly limited, and examples thereof include petroleum ether, hexane, carbon tetrachloride, toluene, benzene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether, or a mixed solution thereof. It is done.

  Specific examples of the organic alkali metal used in the synthesis of the dianion ligand (L2) include methyl lithium, butyl lithium, and phenyl lithium. Particularly, n-butyl lithium is preferable, and the alkoxide having 3 or more carbon atoms. As sodium propoxide, sodium butoxide, potassium propoxide, potassium butoxide and the like, sodium butoxide and potassium butoxide are particularly preferable, among which sodium t-butoxide and potassium t-butoxide are more preferable, and potassium t-butoxide is particularly preferable. Is preferred.

  In addition, the combination of alkoxide and organic alkali metal used is particularly preferably a combination of potassium t-butoxide and n-butyllithium. Next, in the synthesis of the novel transition metal compound (A) represented by the above general formula (1), the dianion ligand represented by the above general formula (3) is dissolved in a solvent and stirred while stirring the above general formula. It can be carried out by reacting (4). The liquid temperature during the reaction is selected in the range of -80 ° C to 120 ° C, but an appropriate reaction temperature is selected according to the progress of the reaction, and it is confirmed that the reaction proceeds at a low temperature. It is preferable to carry out the reaction at a temperature not higher than ° C. On the other hand, when the reaction proceeds slowly, the reaction can be carried out while heating to 25 ° C or higher. The solvent to be used is not particularly limited, and examples thereof include petroleum ether, hexane, carbon tetrachloride, toluene, benzene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether, or a mixed solution thereof. When the by-product is included after completion of the reaction, the usual operation used when purifying the transition metal complex such as extraction and recrystallization is used as a method for purely extracting the target complex. The solvent used for extraction and recrystallization is not particularly limited, and examples thereof include petroleum ether, hexane, carbon tetrachloride, toluene, benzene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether, or a mixed solution thereof. It is done.

  Although the example of the specific structure of the transition metal compound (A) represented by the said General formula (1) obtained by making it above is shown below, it is not limited to these.

  In this specification, the methyl group may be abbreviated as Me, the t-butyl group as t-Bu, the adamantyl group as Ad, the cumyl group as Cum, the trimethylsilyl group as TMS, and the phenyl group as Ph.

[Optional components constituting the olefin polymerization catalyst]
The transition metal compound (A) can be used alone or in combination as a catalyst for olefin polymerization, but the olefin polymerization catalyst according to the present invention can be used as required.
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It may contain at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs. Next, each component of (B) component used as needed is demonstrated.

( B-1) Organometallic Compound Specific examples of the organometallic compound (B-1) include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q (wherein R ^a and R ^b may be the same or different and have 1 to 15 carbon atoms, preferably 1-4 represents a hydrocarbon group, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3 And m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄ (wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A complex alkylated product of a Group 1 metal and aluminum represented by the formula:

(B-1c) General formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) And M ³ is Mg, Zn or Cd.) A dialkyl compound of a Group 2 or Group 12 metal represented by:

  Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). M is preferably a number of 1.5 ≦ m ≦ 3.)
General formula R ^a _m AlX _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,
It is represented by the general formula R ^a _m AlH _3-m (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3). Organoaluminum compounds,
General formula R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b may be the same or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). X represents a halogen atom, m is a number of 0 <m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. Organoaluminum compound.

More specifically, as the organoaluminum compound belonging to (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methyl Pentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum Tri-branched alkylaluminums such as tricyclohexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) tri isoprenylaluminum represented by like Trialkenyl aluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide and the like; Average ^{_{R a 2.5 Al (OR b)}} 0.5 represented by like; mini um methoxide, diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide Partially alkoxylated alkylaluminum with composition: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl- Dialkylaluminum aryloxy such as 4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) De; Dialkylaluminum halides such as methylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; including partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. .

A compound similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  In addition, as the organometallic compound (B-1), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used. Of the organometallic compounds (B-1), organoaluminum compounds are preferred. The organometallic compound (B-1) as described above is used singly or in combination of two or more.

( B-2) Organoaluminum oxy compound The organoaluminum oxy compound ( B-2) used as necessary in the present invention may be a conventionally known aluminoxane or exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound. A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent. [1] Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon. [2] A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl 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.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (for example, Hydrocarbon solvents such as chlorinated products, brominated products, etc.). Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy-compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is Those that are insoluble or sparingly soluble are preferred. Examples of the organoaluminum oxy compound include an organoaluminum oxy compound (G-1) containing boron represented by the following general formula (5).

(In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other. The organoaluminumoxy compound (G-1) containing boron represented by the general formula (5) includes an alkyl boronic acid (G-2) represented by the following general formula (6),

(In the formula, R ²⁰ represents the same group as described above.) By reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. Can be manufactured.

  Specific examples of the alkyl boronic acid (G-2) represented by the general formula (6) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, Examples thereof include n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  The (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.

(B-3) Ionized ionic compound The ionized ionic compound (B-3) is a compound that reacts with the transition metal compound (A) to form an ion pair. Examples of such compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, US5321106, and the like. Etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group, or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

  Examples of the ionic compound include a compound represented by the following general formula (7).

In the formula, ^examples of R ²²⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ may be the same as or different from each other, and each represents an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ²²⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) Ammonia Such as tetra (o- tolyl) boron and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (8) or (9).

（式中、Etはエチル基を示す。）

(In the formula, Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.

Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundeborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammo Nitrobromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri ( n-Butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbaound decaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaound decaborate , Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Salts of anions such as decahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl ) Ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III ), Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri ( n-Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicar Bound Decaborate) Ferrate (III), Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), Tri (n-butyl) ) Ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromic acid Salt (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (Undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV), etc. Examples thereof include salts of metal carborane anions.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, With barium etc. And organic salts such as triphenylethyl salt, and isopoly compounds, and the like. The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

  The ionized ionic compound (B-3) as described above is used singly or in combination of two or more.

Other transition metal compounds In the present invention, in the polymerization, together with the transition metal compound (A), other transition metal compounds such as known ligands containing hetero atoms such as nitrogen, oxygen, sulfur, boron or phosphorus are known. Transition metal compounds can be used in combination.

[Olefin polymerization method]
Olefin is an unsaturated hydrocarbon composed of carbon and hydrogen atoms, specifically, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl- 1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Α-olefins having 2 to 20 carbon atoms such as hexadecene, 1-octadecene, 1-eicosene; olefins containing internal double bonds such as cis-2-butene, trans-2-butene; isobutene, 2-methyl-1 -Pentene, 2,4-dimethyl-1-pentene, 2,4-dimethyl-1-hexene, 2,4,4-trimethyl-1-pe Branched olefins such as styrene, 2,4-dimethyl-1-heptene; cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene; butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4- Octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1, Cyclic or chain dienes or polyenes having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds, such as 7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; Styrene, o-methyl Aromatic vinyl compounds such as styrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; vinylcyclohexane and the like.

  The olefin may have a functional group containing atoms such as oxygen, nitrogen, sulfur and the like. For example, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Unsaturated carboxylic acid metal salts such as salts, magnesium salts and calcium salts; unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Products; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Unsaturated cals such as n-propyl methacrylate, 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; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate Unsaturated glycidyl esters such as; Halogenated olefins such as vinyl chloride, vinyl fluoride and allyl fluoride; Unsaturated cyano compounds such as acrylonitrile and 2-cyano-bicyclo [2.2.1] -5-heptene; Methyl vinyl ether, ethyl Unsaturated ether compounds such as vinyl ether; unsaturated amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate Hydroxystyrene, o- chlorostyrene, p- chlorostyrene, functional group-containing styrene derivatives such as divinyl benzene; and N- vinylpyrrolidone. As the olefin, α-olefin is preferable, and ethylene is particularly preferable.

  In the method for producing an olefin polymer according to the present invention, olefin polymerization is carried out in the presence of a catalyst comprising the above components (A) and (B) and, if necessary, other transition metal compounds. In the polymerization, the method of adding the component (A) to the polymerization vessel, the usage method of each component, the addition method, and the order of addition are arbitrarily selected, and the following methods are exemplified. (1) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order. (2) A method in which a catalyst in which component (A) and component (B) are contacted in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.

  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. Specific 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, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. It can also be used as a solvent.

When the olefin is polymerized using the catalyst as described above, the component (A) is usually 10 ⁻¹³ to 10 ⁻² mol, preferably 10 ⁻¹¹ to 10 ⁻³ mol, per liter of reaction volume. Used in such amounts. Even when the component (A) is used at a relatively low concentration, the olefin can be polymerized with high polymerization activity.

  Component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000.

  Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) usually from 1 to 1. The amount used is 500,000, preferably 10 to 100,000.

  Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount that it becomes 1-5. 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. In the case of component (B-2) in an amount of 1 to 5, the molar ratio of component (D) to aluminum atoms in component (B-2) [(D) / (B-2 )] Is usually 0.001 to 2, preferably 0.005 to 1 in the case of component (B-3), the molar ratio [(D) / (B-3)] is The amount is usually 0.01 to 10, preferably 0.1 to 5.

  There is no restriction | limiting in particular in the quantity of the olefin used for superposition | polymerization, It selects suitably by the kind of olefin to be used, the copolymerization ratio of the copolymer to be obtained, etc.

The polymerization temperature using such a polymerization catalyst is usually in the range of −50 to 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

Preparation of catalyst component << [Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (4,6-di-tert-butylphenoxy)] TiCl ₂ synthesis >>
[Synthesis of 2-Bromo-4,6-di-tert-butylphenol]
2,4-Di-tert-butylphenol (10.00 g, 48.46 mmol) was used for reaction and purification by the method described in Organometallics., 2003 (22), 3877, and the desired 2-Bromo-4,6- 10.51 g of di-tert-butylphenol was obtained (76%, white solid).

[Synthesis of 1-Bromo-3,5-di-tert-butyl-2-methoxy-benzene]
A rotor is placed in a Schlenk-type reaction vessel that has been sufficiently dried and purged with nitrogen, and 2-Bromo-4,6-di-tert-butylphenol (10.51 g, 36.83 mmol) obtained in the above reaction is placed in the reactor, followed by acetonitrile. (30 ml) was added and stirred, potassium hydroxide (2.48 g, 44.20 mmol) was added followed by iodomethane (11.4 ml, 184.15 mmol), and the mixture was reacted at 20 ° C. with stirring for 16 hours. The solvent was distilled off from the reaction solution under reduced pressure, the resulting crude product was extracted with hexane, and the solvent was distilled off from the extract under reduced pressure to obtain the desired 1-Bromo-3,5-di- 10.03 g of tert-butyl-2-methoxy-benzene was obtained (91%, yellow oil).
The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 298 (M +).

[Preparation of Octamethyloctahydrodibenzofluorenyllithium / tetrahydrofuran solution]
A rotor was placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and this was synthesized by the method described in Organometallics., 2004 (23), 1777, 1,1,4,4,7,7,10, 10-octamethyl-1,2,3,4,7,8,9,10-octahydrobenzo [b, h] fluorene (Octamethyloctahydrodibenzofluorene) (6.45g, 16.71mmol) is added, and tetrahydrofuran (100ml) is added and dissolved. N-butyllithium (1.57M in hexane; 10.64 ml, 16.71 mmol) was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 16 hours to obtain a tetrahydrofuran solution of Octamethyloctahydrodibenzofluorenyllithium.

[(3,5-Di-tert-butyl-2-methoxy-phenyl) -dimethyl- (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7, 8,9,10-octahydro-1H-dibenzo [b, h] fluorenyl) -silane [[Synthesis of [Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3,5-di-tert-butyl-2-methoxyphenol)]]
A rotor was placed in a Schlenk-type reaction vessel that had been sufficiently dried and purged with nitrogen, and 1-Bromo-3,5-di-tert-butyl-2-methoxy-benzene (5.00 g, 16.71 mmol) and tetrahydrofuran (100 ml) were added, and n-butyllithium (1.57M in hexane; 22.34 ml, 35.09 mmol) was added dropwise at −78 ° C. with stirring, and the mixture was further reacted at room temperature for 6 hours. The obtained reaction solution was slowly added dropwise to a hexane (100 ml) solution of diphenyldichlorosilane (4.23 g, 16.71 mmol) cooled to −78 ° C., and further reacted at room temperature for 3 hours, and then the solvent was removed from the reaction solution under reduced pressure. Distilled off. Tetrahydrofuran (150 ml) was added to the obtained mixture, and the tetrahydrofuran solution of Octamethyloctahydrodibenzofluorenyllithium obtained in the above reaction was added dropwise at −78 ° C. with stirring. The mixture was further reacted at room temperature for 16 hours, and then an aqueous ammonium chloride solution was added. The organic phase extracted and separated with diethyl ether was dried over magnesium sulfate and filtered, and the solvent was removed from the filtrate under reduced pressure to obtain a solid. This solid was recrystallized from hexane to obtain 3.93 g of desired [[Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3,5-di-tert-butyl-2-methoxyphenol)] (30%, white solid). The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 786 (M +).

[[Synthesis of Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3,5-di-tert-butylphenoxy) Ti Cl ₂ ]
A rotor was placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and obtained by the above reaction [[Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3,5-di-tert-butyl-2-methoxyphenol)] (2.01 g, 2.55 mmol), KO ^t Bu (0.573 g, 5.11 mmol), and hexane (100 ml) were added, and the resulting suspension was obtained with n-butyllithium (1.57M in hexane; 3.25 ml, 5.11 mmol). Hexane (100 ml) was added to the mixed solution at 0 ° C. After completion of the addition, the mixture was reacted at 20 ° C. with stirring for 3 hours, and the resulting mixture was added to a solution of TiCl ₄ (0.484 g, 2.55 mmol) in hexane (20 ml) at 20 ° C. After the addition, the mixture was reacted under reflux to obtain a brown suspension. After concentrating and drying this suspension, the resulting solid was extracted with toluene, filtered through Celite, and the filtrate was concentrated and recrystallized to obtain the desired [[Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3,5- 0.25 g of di-tert-butylphenoxy) TiCl ₂ was obtained (11%, brown solid). The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 888 (M +).

Preparation of catalyst components << [Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3-tert-butyl-5-methylphenoxy)] Ti Cl ₂ synthesis >>
[Synthesis of 2-Bromo-6-tert-butyl-4-methyl-phenol]
2-tert-Butyl-4-methyl-phenol (20.01 g, 121.8 mmol) was dissolved in acetic acid (150 ml), and bromine (22.6 g, 141.4 mmol) was slowly added dropwise thereto. After the reaction with stirring at room temperature for 18 h, saturated sodium sulfate (50 ml) was added, followed by water (100 ml). Diethyl ether was added to the resulting mixture for extraction (50 ml × 2), the organic layer was washed with water (100 ml × 2), and dried by adding sodium sulfate. After removing the solid by filtration, the solvent was distilled off from the furnace liquid under reduced pressure to obtain 25.72 g of the desired 2-Bromo-6-tert-butyl-4-methyl-phenol (87%, pale yellow oil).

The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 242 (M +).
¹ H NMR (CDCl ₃ ): d 7.15 (s, 1H, Ar), 7.00 (s, 1H, Ar), 5.61 (s, 1H, OH), 2.25 (s, 3H, CH ₃ ), 1.38 (s, 9H, C (CH ₃ )).

[Synthesis of 2-Allyloxy-1-bromo-3-tert-butyl-5-methyl-benzene]
Place the rotor in a Schlenk-type reaction vessel that has been thoroughly dried and purged with nitrogen, and put 2-Bromo-6-tert-butyl-4-methyl-phenol (12.28 g, 50.5 mmol) obtained in the above reaction into this. While adding acetonitrile (100 ml) and stirring, potassium hydroxide (3.68 g, 65.7 mmol) was added to obtain a white slurry with a green solution. While this was cooled to 0 ° C., allyl bromide (7.94 g, 65.7 mmol) was added dropwise. After completion of the dropwise addition, the mixture was slowly returned to room temperature and allowed to react at room temperature with stirring for 10 hours. The obtained mixture was filtered, the solvent was distilled off from the furnace liquid under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane) to give the desired 2-Allyloxy-1- 12.69 g of bromo-3-tert-butyl-5-methyl-benzene was obtained (89%, colorless oil).

The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 282 (M +).
¹ H NMR (CDCl ₃ ): d 7.25 (s, 1H, Ar), 7.06 (s, 1H, Ar), 6.12 (m, 1H), 5.48 (d, 1H), 5.29 (d, 1H), 4.56 ( d, 2H, CH ₂ ), 2.27 (s, 3H, CH ₃ ), 1.38 (s, 9H, C (CH ₃ )).

[Preparation of Octamethyloctahydrodibenzofluorenyllithium / tetrahydrofuran solution]
A rotor was placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and this was synthesized by the method described in Organometallics., 2004 (23), 1777, 1,1,4,4,7,7,10, 10-octamethyl-1,2,3,4,7,8,9,10-octahydrobenzo [b, h] fluorene (Octamethyloctahydrodibenzofluorene) (13.65g, 35.31mmol) is added, tetrahydrofuran (100ml) is added and dissolved, N-butyllithium (1.59M in hexane; 22.2 ml, 35.31 mmol) was added dropwise at −78 ° C., and the mixture was further stirred at room temperature for 16 hours to obtain a tetrahydrofuran solution of Octamethyloctahydrodibenzofluorenyllithium.

[(2-Allyloxy-3-tert-butyl-5-methyl-phenyl) -dimethyl- (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7, 8,9,10-octahydrodibenzo [b, h] fluorenyl) -silane [Synthesis of Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (2-Allyloxy-3-tert-butyl-5-methylphenol)]
A rotor was placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and 2-Allyloxy-1-bromo-3-tert-butyl-5-methyl-benzene (10.00 g, 35.31) mmol) and tetrahydrofuran (100 ml) were added, and n-butyllithium (1.59M in hexane; 22.2 ml, 35.31 mmol) was added dropwise at -78 ° C with stirring, and the mixture was allowed to react for 2 hours while maintaining at -78 ° C. While this reaction solution was cooled to −78 ° C., it was transferred to a hexane (100 ml) solution of dimethyldichlorosilane (45.57 g, 35.31 mmol) cooled to −78 ° C. using a Teflon (registered trademark) tube at a nitrogen pressure. After completion of the transfer, the mixture was slowly returned to room temperature, reacted at room temperature with stirring for 15 hours, and then the solvent was distilled off under reduced pressure. Tetrahydrofuran (100 ml) was added to the resulting mixture, and the above reaction was obtained at −78 ° C. with stirring.

A solution of Octamethyloctahydrodibenzofluorenyllithium in tetrahydrofuran (100 ml) was added dropwise. After completion of the addition, the solution was slowly returned to room temperature, allowed to react with stirring at room temperature for 15 hours, and then an aqueous ammonium chloride solution was added. Extraction with hexane, the separated organic phase was dried over sodium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain the desired [Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (2-Allyloxy-3-tert-butyl -5-methylphenol)] was obtained (26%, white solid). The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 646 (M +).

[[Synthesis of Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3-tert-butyl-5-methylphenoxy)] Ti Cl ₂ ]
A rotor was placed in a Schlenk-type reaction vessel that had been sufficiently dried and purged with nitrogen, and [Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (2-Allyloxy-3-tert-butyl-5-methylphenol)] ( 2.66 g, 4.12 mmol), KO ^t Bu (0.925 g, 8.24 mmol), and hexane (100 ml) were added, and the resulting suspension was added to n-butyllithium (1.57M in hexane; 5.25 ml, 8.24 mmol) and hexane. (100 ml) was added to the mixed solution at 0 ° C. After completion of the addition, the mixture was reacted at 20 ° C. with stirring for 3 hours, and the obtained mixture was added to a hexane (20 ml) solution of TiCl ₄ (0.781 g, 4.12 mmol) at 20 ° C. After the addition, the mixture was reacted under reflux to obtain a brown suspension. After concentrating and drying this suspension, the resulting solid was extracted with toluene, filtered through celite, and the filtrate was concentrated and recrystallized to obtain the desired [Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (3-tert-butyl -5-methylphenoxy)] Ti Cl ₂ (0.388 g, 13%, brown solid) was obtained. The result of analyzing the obtained product by FD-MS was as follows. FD-MS: 722 (M +).

<Ethylene polymerization using [Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (4,6-di-tert-butylphenoxy)] Ti Cl ₂ >
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene solution, and the liquid phase and gas phase were saturated with ethylene gas (= 100 liters / hr) at 50 ° C. Thereafter, 0.0125 mmol of triisobutylaluminum and 0.25 ml of a toluene solution (1 mmol / L) of [Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (4,6-di-tert-butylphenoxy)] TiCl ₂ synthesized in Example 1 were added, Subsequently, 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate relative to Ti was added to initiate polymerization. After reacting at 50 ° C. for 0 minutes in an atmosphere of normal pressure ethylene gas (= 100 liters / hr), the polymerization was terminated by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.36 g of polyethylene.

<Ethylene polymerization using [Me ₂ Si (Octamethyloctahydrodibenzofluorenyl) (6-tert-butyl-4-methylphenoxy)] Ti Cl ₂ >
In Example _{3, [Ph 2 Si (Octamethyloctahydrodibenzofluorenyl} ) (4,6-di-tert-butylphenoxy)] Ti Cl synthesized in Example 2 in ₂ of the changes _{[Me 2 Si (Octamethyloctahydrodibenzofluorenyl) (} 6-tert-butyl- Polymerization and post-treatment were performed in the same manner as in Example 1 except that 4-methylphenoxy)] TiCl ₂ was used, to obtain 1.73 g of polyethylene.

[Comparative Example 1]
[[Synthesis of Me ₂ Si (Tetramethylcyclopentadienyl) (6-tert-butyl-4-methylphenoxy)] Ti Cl ₂ ]
A rotor was placed in a Schlenk-type reaction vessel that had been sufficiently dried and substituted with nitrogen, and the [Me ₂ Si (Tetramethylcyclopentadienyl) (1-allyloxy-6-tert-butyl-4-methylphenol) obtained in JP-A-9-87313 was added to this. )] (2.81 g, 7.6 mmol) and toluene (30 ml) were added, and n-butyllithium (1.60M in hexane; 4.8 ml, 7.7 mmol) was added dropwise at −78 ° C. with stirring. The mixture was returned and reacted with stirring at room temperature for 15 hours. The obtained liquid mixture is again cooled to −78 ° C., and slowly added dropwise to a mixed solution of TiCl ₄ (1.0 M in toluene; 7.6 ml, 7.6 mmol) and toluene (30 ml) with stirring. The mixture was returned to room temperature and further reacted with stirring at 90 ° C. for 12 hours to obtain a brown suspension. After the suspension was concentrated and dried, the resulting solid was extracted with toluene, filtered through celite, and the filtrate was concentrated to obtain a brown solid. The obtained product was analyzed by ¹ H-NMR and FD-MS, but none of the desired products could be confirmed.

[Comparative Example 2]
<Ethylene polymerization using Cp ₂ TiCl ₂ >
In Example 1, instead of [Ph ₂ Si (Octamethyloctahydrodibenzofluorenyl) (4,6-di-tert-butylphenoxy)] Ti Cl ₂ , 0.25 ml of a toluene solution (1 mmol / l) of Cp ₂ TiCl ₂ was used. In place of aluminum and triphenylcarbenium tetrakis (pentafluorophenyl) borate, 0.0625 mmol of dry MAO, reaction temperature was changed to 75 ° C., and the reaction time was changed to 5 minutes. As a result, 0.78 g of polyethylene was obtained.

When the novel transition metal compound according to the present invention is used as a catalyst component for olefin polymerization, polymerization proceeds with high polymerization activity. Further, when copolymerization is performed, an ethylene / olefin copolymer having a high comonomer content can be obtained when a small amount of comonomer is used as compared with a conventional olefin polymerization catalyst, which is extremely valuable industrially.

Claims (25)

A transition metal compound (A) having a structure represented by the following general formula (1).

[In General Formula (1), M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and the atoms or groups represented by R ^{1 to} R ⁸ are a hydrogen atom, a halogen atom, a hydrocarbon group, A group selected from a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, which may be the same or different from each other, but R ³ and R ⁶ are not hydrogen at the same time, R ¹ Two groups adjacent to each other among the atoms or groups represented by ˜R ⁸ may be bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded; ^{9 to} R ¹² may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ^8, and two adjacent groups among the atoms or groups represented by R ^{9 to} R ¹² are Combine to form an aromatic, aliphatic, or heterocyclic ring with their attached carbon atoms It may be. Q represents a carbon atom, a silicon atom, boron, aluminum, gallium, indium, or thallium, and R ¹³ and R ¹⁴ may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ⁸ Two of the atoms or groups represented by R ¹³ and R ¹⁴ may be bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. Good. X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and D represents —O—, —S—, —NR ^a —, — PR ^b- represents, and R ^a and R ^b represent a hydrogen atom or a hydrocarbon group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are the same as each other However, they may be different, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a nonconjugated linear diene, or a nonconjugated branched diene. In addition, a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a nonconjugated cyclic diene, and n Represents an integer of 0 to 3. ]   The valence state of the transition metal atom M in the general formula (1) is a transition metal atom of Group 4 or Group 5 of the periodic table which is divalent, trivalent or tetravalent. The transition metal compound (A) described in 1. The transition metal compound (A) according to claim 1 or 2, wherein R ² and R ³ are not both hydrogen, or R ⁶ and R ⁷ are not both hydrogen. R ² and R ³ are bonded to each other, or R ⁶ and R ⁷ are bonded to each other to form an aliphatic ring or a heterocyclic ring together with the carbon atom to which these groups are bonded. The transition metal compound (A) according to claim 3. R ² and R ³ are bonded to each other, or R ⁶ and R ⁷ are bonded to each other, and together with the carbon atom to which the groups are bonded, 1,1,4,4-tetramethyl-1,2,3, The transition metal compound (A) according to claim 4, wherein a 4-tetrahydrobenzo [b] fluorenyl group is formed. The transition metal compound (A) according to claim 1, wherein R ³ and R ⁶ are not both hydrogen. The transition metal compound (A) according to claim 6, wherein any of R ² , R ³ , R ⁶ and R ⁷ is not hydrogen. R ² and R ³ are bonded to each other, and R ⁶ and R ⁷ are bonded to each other to form an aliphatic ring or a heterocycle together with the carbon atom to which the groups are bonded, The transition metal compound (A) according to claim 7. R ² and R ³ are bonded to each other, and R ⁶ and R ⁷ are bonded to each other to form 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7 , 8,9,10-octahydrobenzo [b, h] fluorenyl group is formed, The transition metal compound (A) according to claim 8, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silylated hydrocarbon group having 1 to 20 carbon atoms, The transition metal compound (A) in any one. The transition metal compound (A) according to claim 10, wherein R ⁹ is a tertiary hydrocarbon group or a tertiary silylated hydrocarbon group. The transition metal compound (A) according to claim 10, wherein R ⁹ is an aromatic substituted aliphatic group, an aromatic group or an alicyclic group. The transition metal compound (A) according to claim 1, wherein Q is a carbon atom or a silicon atom.   The transition metal compound (A) according to claim 1, wherein D is oxygen.   The transition metal compound (A) according to claim 1, wherein M is a transition metal atom selected from Group 4 of the periodic table. The neutral ligand (L1) represented by the following general formula (2), which is a precursor of the transition metal compound (A), is converted into a dianion ligand (L2) represented by the following general formula (3) Then, a transition metal compound (A) is produced by reacting a transition metal compound represented by the following general formula (4), wherein the neutral ligand (L1) is converted to a dianion ligand ( The step of converting to L2) includes a step of preparing a dianion ligand (L2) by reacting an organic alkali metal in the presence of an alkoxide having 3 or more carbon atoms. The manufacturing method of the transition metal compound (A) in any one of.

[In General Formula (2), General Formula (3), and General Formula (4), R ^{1 to} R ¹⁴ , M, Q, D, X, Y, and m and n are in the general formula (1). And R ¹⁵ represents the same atom or group as R ^{1 to} R ⁸ described above. ]
The method for producing a transition metal compound (A) according to claim 16, wherein the alkoxide is potassium butoxide and the organic alkali metal is butyl lithium.
The transition metal compound (A) according to any one of claims 1 to 15,
(B) (B-1) Organometallic compound
(B-2) an organoaluminum oxy compound, and
(B-3) An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs.   An olefin polymerization method comprising homopolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 18. The olefin polymerization method according to claim 19, wherein two or more kinds of olefins are copolymerized.   The olefin polymerization method according to claim 19 or 20, wherein the olefin has a branched structure.   The olefin polymerization method according to claim 19 or 20, wherein the olefin has an internal olefin structure.   The olefin polymerization method according to claim 19 or 20, wherein the olefin is a cyclic or chain conjugated or non-conjugated diene or a conjugated or non-conjugated polyene having two or more double bonds. .   The olefin polymerization method according to claim 19 or 20, wherein the olefin is an aromatic vinyl compound. A method for producing an ethylene polymer having an alkyl side chain in the method for homopolymerizing ethylene in the presence of the olefin polymerization catalyst according to claim 18.