JP2018162231A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel transition metal compound used for a catalyst for olefin polymerization that makes it possible to exploit the performances useful for the high functionalization of an olefin polymer.SOLUTION: The present invention provides a transition metal compound of general formula (1), a catalyst for olefin polymerization containing the same, and a method for producing an olefin polymer with the catalyst (where M is a transition metal atom in the periodic table groups 3-10, R-Rare a hydrogen atom or the like, Cand Care a carbon atom, D is an oxygen atom having a substituent, or the like, Land Lare an oxygen atom or the like, Eand Eare a linking group, n is a valence of M, X is a halogen atom or the like).SELECTED DRAWING: None

Description

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

  Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium compound and an organoaluminum compound. Vanadium-based catalysts are known. A metallocene catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

  In recent years, various postmetallocene catalysts have been reported as next-generation olefin polymerization catalysts (for example, Non-Patent Document 1). In the technical field of olefin polymerization catalysts, it is very important to research and provide highly active and highly functional postmetallocene catalysts. Among these, post-metallocene catalysts with multidentate ligands are attractive in terms of their stability and functionality, but there are few known catalysts that are truly highly active in the industrial sense. Development is strongly desired.

  On the other hand, the present applicant has found that transition metal compounds having a phenoxyimine ligand have various functions in olefin polymers obtained by increasing the activity of olefin polymerization catalysts by converting the ligand skeleton and substituents. And have already been found to be able to impart features (for example, Non-Patent Document 2).

Chemical Reviews 2003, 103, 283-315. Chemical Reviews 2011, 111, 2363-2449.

  As described above, as a multidentate post metallocene catalyst, a catalyst with a truly high activity in an industrial sense is not well known. It is also necessary to draw out performance that makes use of the multidentate catalyst, particularly useful for enhancing the functionality of the olefin polymer.

  An object of the present invention is to provide a novel transition metal compound used for an olefin polymerization catalyst that can bring out a performance that is useful for enhancing the functionality of an olefin polymer, an olefin polymerization catalyst containing the transition metal compound, and An object of the present invention is to provide a method for producing an olefin polymer using this catalyst.

  As a result of intensive studies to achieve the above object, the present inventors have shown that an olefin polymerization catalyst comprising a specific transition metal compound that is a multidentate ligand and has a phenoxy ether skeleton exhibits excellent olefin polymerization activity. As a result, the present invention has been completed. That is, the present invention relates to the following [1] to [7].

[1] A transition metal compound (A) represented by the following general formula (1).

(In General Formula (1), M represents a transition metal atom in Groups 3 to 10 of the periodic table.
R ^{1 to} R ³ may be the same as or different from each other, and are 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{1 to} R ³ may be connected to each other to form a ring, and the ring is further substituted It may have a group.
C ¹ and C ² represent carbon atoms.
D is an oxygen atom having one substituent R ⁴ (structure represented by OR ⁴ ), a sulfur atom having one substituent R ⁴ (structure represented by SR ⁴ ), and two substituents R ⁴ nitrogen atom having ^{(N (structure} represented by R _{4) 2),} or represents the substituent ^{R 4} two having phosphorus atom ^{(P (structure} represented by R _{4) 2),} ^{R 4} is hydrogen Indicates an atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group When a plurality of R ⁴ are present, they may be the same or different from each other, and two or more may be connected to each other to form a ring, and the ring may further have the above substituents. .
L ¹ and L ² may be the same or different from each other, and an oxygen atom, a sulfur atom, a nitrogen atom having a substituent R ⁵ (structure represented by NR ⁵ ), or a phosphorus atom having a substituent R ⁵ (Structure represented by PR ⁵ ) wherein R ⁵ is 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
E ¹ and E ² may be the same or different from each other, and each represents a linking group containing at least one carbon atom, silicon atom or germanium atom connecting C ¹ and L ¹ , C ² and L ² , The group may further have a substituent included in the definition of R ^{1 to} R ⁵ .
n represents the valence of M.
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when a plurality of Xs are present, they may be the same as or different from each other, and two or more may be linked to each other to form a ring. )

[2] The transition according to [1], wherein in the general formula (1), C ¹ -E ¹ -L ¹ and C ² -E ² -L ² form a structure represented by the following general formula (2). Metal compound (A).

(In the general formula (2), Q ¹ and Q 2 may be the same as or different from each other, and represent a carbon atom, a silicon atom, or a germanium atom.
y is the number of Q ¹ and z is the number of Q ² , which may be the same as or different from each other, and represents 0 or an integer of 1 to 5. When y and z are 0, C ¹ and C ² and the benzene ring are directly bonded. When y and z are integers of 2 to 5, a plurality of adjacent Q ¹ and Q ² are bonded to each other to form a single bond or a double bond. In the case of forming a double bond, there is no substituent of A ² or A ⁴ in Q ¹ or Q ² forming the double bond.
R ^{6 to} R ¹³ may be the same as or different from each other, and are 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them may be connected to each other to form a ring, and the ring further has the above substituents May be.
When y and z are 1 to 5, that is, when Q ¹ and Q ² are present, A ^{1 to} A ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic group. Indicates a compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these are linked to each other May form a ring, and the ring may further have the above substituent. )

[3] The transition metal compound (A) according to [2], wherein y and z are 0 or 1.

[4] The transition metal compound (A) according to any one of [1] to [3], wherein M is a transition metal atom of Group 4 of the periodic table and n is 4.

[5] An olefin polymerization catalyst comprising the transition metal compound (A) according to any one of [1] to [4].

[6] In addition to the transition metal compound (A),
(B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and
(B-3) a compound that reacts with the transition metal compound (A) to form an ion pair,
The olefin polymerization catalyst according to [5], which contains at least one compound selected from the group consisting of:

[7] A method for producing an olefin polymer, wherein an olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst according to [5] or [6].

  In the present invention, the term “polymerization” is used to mean “homopolymerization” and “copolymerization”. Further, the term “polymer” is used in the meaning including “homopolymer” and “copolymer”.

  The transition metal compound of the present invention is excellent in electron transfer capability and has a chemically stable phenoxy ether structure. Therefore, when this transition metal compound is used as a catalyst for olefin polymerization, it exhibits high olefin polymerization activity.

<Transition metal compound (A)>
The transition metal compound of the present invention (hereinafter referred to as transition metal compound (A)) is represented by the following general formula (1).

  In the general formula (1), M represents a transition metal atom in Groups 3 to 10 of the periodic table (Group 3 includes lanthanoids), preferably Group 3 to 9 (Group 3 also includes lanthanoids). Transition metal atoms, more preferably a transition metal atom selected from Group 3-6, particularly preferably a transition metal atom selected from Group 4 or Group 6, most preferably a Group 4 transition metal atom. is there. Specifically, scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, rhenium atom, iron atom, ruthenium atom, Cobalt atom, rhodium atom, iridium atom, nickel atom, palladium atom, platinum atom, etc., preferably scandium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, Tungsten atom, cobalt atom, rhodium atom, iridium atom, more preferably titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum Child, a tungsten atom, particularly preferably titanium atom, zirconium atom, hafnium atom, chromium atom, tantalum atom, and most preferably titanium atom, zirconium atom, hafnium atom.

In the general formula (1), R ^{1 to} R ³ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{1 to} R ³ may be connected to each other to form a ring. The ring may further have the above substituents.
Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, and an n-hexyl group. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as a vinyl group, an allyl group, and an isopropenyl group. A linear or branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms, such as a cyclohexyl group and an adamantyl group; a cyclopentadienyl group, an inde A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as a ru group or a fluorenyl group; 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group or an anthracenyl group, preferably 6-20 aryl groups; alkyl-substituted aryl groups such as tolyl group, iso-propylphenyl group, tert-butylphenyl group, dimethylphenyl group, di-tert-butylphenyl group, tri-iso-propylphenyl group; It is done.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples of the hydrocarbon group in which such a hydrogen atom is substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. The hydrocarbon group may be substituted with other hydrocarbon groups, and examples of the hydrocarbon group substituted with such a hydrocarbon group include aryl groups such as a benzyl group, a cumyl group, and a trityl group. A substituted alkyl group is mentioned.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as luphonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphorus-containing groups such as phosphide group, phosphoryl group, thiophosphoryl group, phosphato group; A germanium-containing group; or a tin-containing group.

  Examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole, and phenanthroline, oxygen-containing compounds such as furan, pyran, benzofuran, and benzopyran, and sulfur-containing compounds such as thiophene and benzothiophene. Residues such as compounds, and groups obtained by further substituting substituents such as alkyl groups, alkoxy groups and aryl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, on these heterocyclic compound residues It is done.

  Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group. Group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-tert-butylsilyl group, dimethyl (pentafluorophenyl) silyl group, tribenzylsilyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group, a tribenzylsilyl group, and the like are preferable. Group, triphenylsilyl group, dimethylphenylsilyl group and tribenzylsilyl group are preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, and a tribenzylsiloxy group.

  Examples of the germanium-containing group or the tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium or tin.

As described above, R ^{1 to} R ³ can be an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, or a phosphorus-containing group. Examples of these include the hydrocarbon group described above. Also, the same groups as those described above may be mentioned.

  Among the oxygen-containing groups, specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group. Specifically, phenoxy group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,5-di-tert-butylphenoxy group and the like can be mentioned. Examples include an oxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and the like, specifically as an acyl group, a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, p -A methoxybenzoyl group etc. are mentioned.

  Among the nitrogen-containing groups, specific examples of the amino group include dimethylamino group, ethylmethylamino group, diphenylamino group and the like, and specific examples of imino group include methylimino group, ethylimino group, propylimino group, butyrimino group. Group, phenylimino group, and the like. Specific examples of the amide group include an acetamido group, N-methylacetamido group, and N-methylbenzamide group. Specific examples of the imide group include acetamido group and benzimide group. Etc.

  Among the sulfur-containing groups, specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group. Specific examples of the alkylthio group include a methylthio group and an ethylthio group. Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group. Specific examples of the sulfonamido group include a phenylsulfonamido group, an N-methylsulfonamido group, and an N-methyl-p-toluenesulfonamido group.

R ^{1 to} R ³ are preferably a hydrogen atom, a hydrocarbon group, or a heterocyclic compound residue, and more preferably a hydrogen atom or a hydrocarbon group. Particularly, the hydrocarbon group is a carbon atom such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, and n-hexyl group. A linear or branched alkyl group having 1-30, preferably 1-20; 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably An aryl group having 6 to 20 atoms; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; A substituted aryl group substituted with 1 to 5 substituents such as an aryloxy group is preferred.

  Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole and phenanthroline, oxygen-containing compounds such as furan, pyran, benzofuran and benzopyran, and sulfur-containing compounds such as thiophene and benzothiophene. Residues such as compounds, and groups obtained by further substituting substituents such as alkyl groups, alkoxy groups and aryl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, on these heterocyclic compound residues are preferred.

Two or more groups of R ^{1 to} R ^{3 in} the general formula (1) may be connected to each other to form a ring. More specifically, two or more groups of R ^{1 to} R ³ , preferably adjacent groups, are linked to each other, an aliphatic ring, an aromatic ring, a hetero ring containing a hetero atom such as a nitrogen atom, etc. These rings may further have a substituent.

In the general formula (1), C ¹ and C ² represent carbon atoms.

In the general formula (1), D represents an oxygen atom having one substituent R ⁴ (structure represented by OR ⁴ ), a sulfur atom having one substituent R ⁴ (structure represented by SR ⁴ ), A nitrogen atom having two substituents R ⁴ (structure represented by N (R ⁴ ) ₂ ) or a phosphorus atom having two substituents R ⁴ (structure represented by P (R ⁴ ) ₂ ) Show. The definition of R ⁴ is the same as R ^{1 to} R ^3, and the same substituents as those exemplified for R ^{1 to} R ³ can be selected, and is preferably a hydrocarbon group. As D, an oxygen atom having one substituent R ⁴ is particularly preferable.

In the general formula (1), L ¹ and L ² may be the same as or different from each other, and an oxygen atom, a sulfur atom, a nitrogen atom having a substituent R ⁵ (structure represented by NR ⁵ ), or a substituent It shows the (structure represented by PR ⁵⁾ phosphorus atoms having the group ^{R 5.} The definition of R ⁵ is the same as R ^{1 to} R ^3, and the same substituents as those exemplified for R ^{1 to} R ³ can be selected, and preferably an oxygen atom or a nitrogen atom having a substituent R ⁵ is there.

In the general formula (1), the bond between D and M, L ¹ and M, and L ² and M is a covalent bond or a coordinate bond depending on the type of transition metal atom M (group of the periodic table). Further, even when the presence or absence of a bond between D and M, L ¹ and M, or L ² and M is not clear, it is treated as a transition metal compound in the present invention.

In the general formula (1), E ¹ and E ² may be the same as or different from each other, and each include at least one carbon atom, silicon atom, or germanium atom that connects C ¹ and L ¹ , and C ² and L ^2. A linking group is shown. This linking group may further have a substituent included in the definition of R ^{1 to} R ⁵ . For example, an optionally substituted hydrocarbon group, a hydrocarbon group in which all or part of the carbon atoms are replaced with silicon atoms, or a hydrocarbon group in which all or part of the carbon atoms are germanium Examples thereof include those substituted with atoms. As the substituent, the same substituents as those exemplified for R ^{1 to} R ³ described above can be selected.
Furthermore, when E ¹ and E ² are expressed as C ¹ -E ¹ -L ¹ and C ² -E ² -L ² structures, it is preferable to form a structure represented by the following general formula (2). .

In the general formula (2), Q ¹ and Q ² may be the same as or different from each other, and represent a carbon atom, a silicon atom, or a germanium atom.

In the general formula (2), y is the number of Q ¹ and z is the number of Q ² , which may be the same or different, and represents 0 or an integer of 1 to 5. When y and z are 0, C ¹ and C ² are in a form in which a benzene ring is directly bonded. When y and z are integers of 2 to 5, a plurality of adjacent Q ¹ and Q ² are bonded to each other to form a single bond or a double bond. In the case of forming a double bond, there is no substituent of A ² or A ⁴ in Q ¹ or Q ² forming the double bond. y and z are preferably 0 or 1.

In the general formula (2), R ^{6 to} R ¹³ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. Group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group. Two or more of these may be connected to each other to form a ring, and the ring may further have a substituent. Specific examples of R ^{6 to} R ¹³ include the same examples as those exemplified for R ^{1 to} R ³ in the general formula (1). Among these, R ^{6 to} R ¹³ are preferably a hydrogen atom, a hydrocarbon group, or a heterocyclic compound residue. Specific examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ³ . Preferable examples of the heterocyclic compound residue include the same as those exemplified as preferred embodiments for R ^{1 to} R ³ .

When y and z are 1 to 5, that is, when Q ¹ and Q ² are present, A ^{1 to} A ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic group. A 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 is shown, and a hydrogen atom or a hydrocarbon group is preferable. Specific examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ³ .

  In the general formula (1), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic ring. A formula compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group is shown.

  Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ³ . Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group, and eicosyl group; carbon such as cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group A cycloalkyl group having 3 to 30 atoms; an alkenyl group such as a vinyl group, a propenyl group and a cyclohexenyl group; an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group; a phenyl group, a tolyl group and a dimethylphenyl group And aryl groups such as trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group. However, the hydrocarbon group is not limited to these. In addition, these hydrocarbon groups include halogenated hydrocarbon groups, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Of these, the halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having 1 to 10 carbon atoms.

  Specific examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an aryloxy group such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group; a phenylmethoxy group And arylalkoxy groups such as phenylethoxy group; acetoxy group; carbonyl group. However, it is not limited to these.

Specific examples of the sulfur-containing group include the same as those exemplified for R ^{1 to} R ³ . Specifically, methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group, benzyl sulfonate group, p-toluene sulfonate group, trimethylbenzene sulfonate group, triisobutylbenzene sulfonate. Sulfonate groups such as nate group, p-chlorobenzene sulfonate group, pentafluorobenzene sulfonate group; methyl sulfinate group, phenyl sulfinate group, benzyl sulfinate group, p-toluene sulfinate group, Examples thereof include sulfinate groups such as trimethylbenzene sulfinate group and pentafluorobenzene sulfinate group; alkylthio group; arylthio group. However, it is not limited to these.

Specific examples of the nitrogen-containing group include the same groups as those exemplified for R ^{1 to} R ³ . Specifically, amino group; alkylamino group such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group; phenylamino group, diphenylamino group, ditolylamino group, dinaphthyl An arylamino group such as an amino group and a methylphenylamino group or an alkylarylamino group can be mentioned. However, it is not limited to these.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). However, it is not limited to these.

  Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tolylphosphine group; methylphosphite group, Examples thereof include phosphite groups (phosphide groups) such as ethyl phosphite group and phenyl phosphite group; phosphonic acid groups; phosphinic acid groups. However, it is not limited to these.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ . However, it is not limited to these.

Specific examples of the heterocyclic compound residue include the same as those exemplified for R ^{1 to} R ³ .

Specific examples of the silicon-containing group include the same groups as those exemplified for R ^{1 to} R ³ . Specifically, phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group, etc. Hydrocarbon-substituted silyl groups; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl groups; silicon-substituted aryl groups such as trimethylsilylphenyl groups.

Specific examples of the germanium-containing group include the same groups as those exemplified for R ^{1 to} R ³ . Specifically, a group in which silicon of the silicon-containing group is replaced with germanium is exemplified.

Specific examples of the tin-containing group include the same ones as exemplified for R ^{1 to} R ³ . Specifically, a group in which silicon in the silicon-containing group is substituted with tin is exemplified.

  Of these, X is preferably a halogen atom or a hydrocarbon group.

  In the general formula (1), n represents the valence of M, specifically a number satisfying the valence. n is usually an integer of 3 to 7, preferably an integer of 3 to 6, more preferably 3 or 4, and particularly preferably 4. When n is 4 or more, plural Xs may be the same or different from each other, and two or more Xs may be connected to each other to form a ring.

  Hereinafter, specific examples of the transition metal compound (A) represented by the general formula (1) are shown. However, the transition metal compound (A) is not limited to these.

  In the above examples, Me represents a methyl group, tBu represents a tertiary butyl group, and Ad represents an adamantyl group. In the above examples, a transition metal compound in which a zirconium atom is replaced with a titanium atom or a hafnium atom can also be mentioned as a preferred example of the transition metal compound (A).

  The manufacturing method of such a transition metal compound (A) is not specifically limited, For example, it can manufacture as follows.

  First, the ligand constituting the transition metal compound (A) is, for example, Suzuki-Miyaura coupling reaction between 2-halogenated alkoxyaryls and boronic acid derived from protected phenols, and further obtained alkoxy It can be obtained by deprotection by Suzuki-Miyaura coupling reaction with boronic acid derived from halogenated and reprotected phenols.

  Suzuki-Miyaura coupling reaction of 2-halogenated alkoxyaryls with boronic acids derived from protected phenols specifically includes these compounds and basic compounds, palladium catalysts as catalysts, ligands of palladium catalysts Solvent 1 is added to the resulting mixture of compounds. These may be dissolved in a solvent or not, and a compound serving as a ligand may or may not be added.

  Examples of the basic compound include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate. Absent.

  Specific examples of the palladium catalyst include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) (chloroform) dipalladium, palladium chloride, palladium acetate, dichlorobis (acetonitrile) palladium, Examples include, but are not limited to, dichlorobis (benzonitrile) palladium and allylpalladium chloride dimer.

  Specific examples of the compound serving as a ligand of the palladium catalyst include tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butyl (methyl) phosphine, 2- (dicyclohexylphosphino) biphenyl, and 2-dicyclohexylphosphino. Phosphine compounds such as -2 '-(dimethylamino) biphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, and Examples include salts of phosphine compounds such as di-tert-butyl (methyl) phosphonium salt of tetrafluoroborate, but are not limited thereto.

  Further, complex compounds of the above phosphine compounds and palladium, such as dichlorobis (tricyclohexylphosphine) palladium, and {1,3-bis (2,6-diisopropylphenyl) imidazolidene} (3-chloropyridyl) palladium dichloride A complex compound of carbene type compound and palladium as described above may be used as a catalyst.

  As the solvent 1, those generally used for such a reaction can be used. Among them, tetrahydrofuran (THF), dimethoxyethane, 1,4-dioxane, N, N-dimethylformamide (DMF), ethanol, propanol and the like can be used. A polar solvent or a hydrocarbon solvent such as toluene or xylene is preferred. Moreover, what added water to the said solvent may be used as a solvent, and it is preferable that water / solvent ratio is 0 / 100-25 / 75 as a mixing ratio.

  As the 2-halogenated alkoxyaryls, commercially available products can be used as they are, but when they are synthesized, they can be obtained, for example, by alkylating 2-halogenated phenols. Specifically, 2-halogenated phenols, a basic compound and an alkylating agent are mixed in the solvent 2.

  Specific examples of 2-halogenated phenols include 2-chlorophenol, 2-bromophenol, 2-iodophenol, 2-bromo-4-tert-butylphenol, and 2-bromo-4-phenylphenol. This is not the case.

  Examples of the basic compound include, but are not limited to, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide and the like.

  Specific examples of the alkylating agent include, but are not limited to, dimethyl sulfate, methyl iodide, dimethyl carbonate, diethyl carbonate, bromopropane, bromobutane, and isobutene.

  Specific examples of the solvent 2 include, but are not limited to, acetone, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the like.

  Boronic acid derived from protected phenols can be synthesized by lithiation with an alkyllithium reagent in solvent 3 and then adding a boronic ester.

  Specific examples of the alkyl lithium reagent include, but are not limited to, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide, and the like. Further, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), hexamethylphosphoric triamide (HMPA) or the like may be added as an activator, and these may be used in a solvent amount.

  Specific examples of the boronic acid ester include, but are not limited to, trimethoxyboronic acid, triethoxyboronic acid, triisopropoxyboronic acid, and the like.

  Specific examples of the solvent 3 include diethyl ether, tetrahydrofuran (THF), tert-butyl methyl ether (TBME), cyclopentyl methyl ether (CPME), and the like, but are not limited thereto.

  The protection of phenols is carried out, for example, according to a conventional method. Protecting groups include tert-butyl group, trityl group, benzyl group, p-methoxybenzyl group, methoxymethyl group, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triisopropylsilyl group Group, methanesulfonyl group, acetyl group, pivaloyl group, 2,2,2-trichloroethoxycarbonyl group, and allyloxycarbonyl group, but not limited thereto.

  As the phenols, commercially available products can be used as they are, but when they are synthesized, for example, they can be obtained by a Suzuki-Miyaura coupling reaction of 2-halogenated phenols and arylboronic acids. Specifically, the solvent 4 is added to a mixture of 2-halogenated phenols, aryl boronic acid, a basic compound, a palladium catalyst as a catalyst, and a compound serving as a ligand of the palladium catalyst. These may be dissolved in the solvent 4 or not, and a compound serving as a ligand may or may not be added.

  Specific examples of 2-halogenated phenols include 2-chlorophenol, 2-bromophenol, 2-iodophenol, 2-bromo-4-tert-butylphenol, and 2-bromo-4-phenylphenol. This is not the case.

  Specific examples of arylboronic acids include phenylboronic acid, o-methylphenylboronic acid, m-methylphenylboronic acid, p-methylphenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, 1-anthraceneboron Acid, 2-anthraceneboronic acid, 9-anthraceneboronic acid, 1-phenanthreneboronic acid, 2-phenanthreneboronic acid, 3-phenanthreneboronic acid, 4-phenanthreneboronic acid, 9-phenanthreneboronic acid, 3,5-di- Examples include, but are not limited to, tert-butyl-phenylboronic acid, mesitylboronic acid, 2,4,6-triisopropylphenylboronic acid, 4-methoxyboronic acid, 4-trifluoromethylphenylboronic acid.

  Examples of the basic compound include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate. Absent.

  Specific examples of the palladium catalyst include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) (chloroform) dipalladium, palladium chloride, palladium acetate, dichlorobis (acetonitrile) palladium, Examples include, but are not limited to, dichlorobis (benzonitrile) palladium and allylpalladium chloride dimer.

  Specific examples of the compound serving as a ligand of the palladium catalyst include tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butyl (methyl) phosphine, 2- (dicyclohexylphosphino) biphenyl, and 2-dicyclohexylphosphino. Phosphine compounds such as -2 '-(dimethylamino) biphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, and Examples include salts of phosphine compounds such as di-tert-butyl (methyl) phosphonium salt of tetrafluoroborate, but are not limited thereto.

  Further, complex compounds of the above phosphine compounds and palladium, such as dichlorobis (tricyclohexylphosphine) palladium, and {1,3-bis (2,6-diisopropylphenyl) imidazolidene} (3-chloropyridyl) palladium dichloride A complex compound of carbene type compound and palladium as described above may be used as a catalyst.

  As the solvent 4, those commonly used for such a reaction can be used, and among them, tetrahydrofuran (THF), dimethoxyethane, 1,4-dioxane, N, N-dimethylformamide (DMF), ethanol, propanol, etc. A polar solvent or a hydrocarbon solvent such as toluene or xylene is preferred. Moreover, what added water to the said solvent may be used as a solvent, and it is preferable that water / solvent ratio is 0 / 100-25 / 75 as a mixing ratio.

  As halogenating agents for alkoxyaryls obtained by Suzuki-Miyaura coupling reaction of 2-halogenated alkoxyaryls with boronic acids derived from protected phenols, specifically bromine, N-bromosuccinimide, Examples include, but are not limited to, 1,2-dibromoethane, iodine, N-iodosuccinimide, 1,2-diiodoethane, and the like.

  The Suzuki-Miyaura coupling reaction of boronic acids derived from halogenated alkoxyaryls and protected phenols specifically becomes these compounds and basic compounds, palladium catalysts as catalysts, and ligands for palladium catalysts. Solvent 5 is added to the compound mixture. These may be dissolved in a solvent or not, and a compound serving as a ligand may or may not be added.

  Examples of the basic compound include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate. Absent.

  Specific examples of the palladium catalyst include bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, tris (dibenzylideneacetone) (chloroform) dipalladium, palladium chloride, palladium acetate, dichlorobis (acetonitrile) palladium, Examples include, but are not limited to, dichlorobis (benzonitrile) palladium and allylpalladium chloride dimer.

  Specific examples of the compound serving as a ligand of the palladium catalyst include tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butyl (methyl) phosphine, 2- (dicyclohexylphosphino) biphenyl, and 2-dicyclohexylphosphino. Phosphine compounds such as -2 '-(dimethylamino) biphenyl, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl, and Examples include salts of phosphine compounds such as di-tert-butyl (methyl) phosphonium salt of tetrafluoroborate, but are not limited thereto.

  Further, complex compounds of the above phosphine compounds and palladium, such as dichlorobis (tricyclohexylphosphine) palladium, and {1,3-bis (2,6-diisopropylphenyl) imidazolidene} (3-chloropyridyl) palladium dichloride A complex compound of carbene type compound and palladium as described above may be used as a catalyst.

As the solvent 5, those commonly used for such a reaction can be used, and among them, tetrahydrofuran (THF), dimethoxyethane, 1,4-dioxane, N, N-dimethylformamide (DMF), ethanol, propanol and the like can be used. A polar solvent or a hydrocarbon solvent such as toluene or xylene is preferred. Moreover, what added water to the said solvent may be used as a solvent, and it is preferable that water / solvent ratio is 0 / 100-25 / 75 as a mixing ratio.
Subsequently, when a protecting group is eliminated with a deprotecting agent such as hydrochloric acid or p-toluenesulfonic acid, a ligand is obtained.

  Next, the corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with the transition metal M-containing compound. Specifically, the synthesized ligand is dissolved in a solvent and, if necessary, contacted with a base to prepare an anion, and then a metal compound such as a metal halide, metal alkylate, metal amidide and the like at a low temperature. Mix and stir for about 1-48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those commonly used in such a reaction can be used, and among them, polar solvents such as diethyl ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene, and dichloromethane are preferably used. Examples of the base used in preparing the anion body include metal salts such as lithium salts such as n-butyl lithium, sodium salts such as sodium hydride, triethylamine, pyridine and the like. Not as long.

Depending on the properties of the compound, the corresponding transition metal compound can also be synthesized by directly reacting the ligand and the metal compound without going through the preparation of the anion body. Further, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. For example, when one or more of R ^{1 to} R ¹³ are hydrogen, a substituent other than hydrogen can be introduced at any stage of the synthesis.

  Moreover, the reaction solution of a ligand and a metal compound can be used as it is without isolating the transition metal compound.

<Olefin polymerization catalyst>
The catalyst for olefin polymerization of the present invention is a catalyst containing the transition metal compound (A) represented by the general formula (1) described above. This catalyst further comprises (B) a compound (B-3) which reacts with an organometallic compound (B-1), an organoaluminum oxy compound (B-2) and a transition metal compound (A) to form an ion pair. It is preferable to include at least one compound selected from the group. In the present specification, the olefin refers to a hydrocarbon having one carbon / carbon double bond in the molecule.

  Hereinafter, the compound (B) will be described in detail.

[Compound (B)]
The catalyst for olefin polymerization of the present invention reacts with (B) organometallic compound (B-1), organoaluminum oxy compound (B-2), and transition metal compound (A) in addition to transition metal compound (A). It is preferable from the viewpoint of polymerization activity that it further contains at least one compound selected from the compound (B-3) that forms an ion pair. Hereinafter, the compounds (B-1), (B-2), and (B-3) will be described.

((B-1) Organometallic compound)
Specific examples of the organometallic compound (B-1) include organometallic compounds represented by the following general formulas (B-1a), (B-1b), and (B-1c).

^{_{R a p Al (OR b)}} q H r Y s ··· (B-1a)
(In the general formula (B-1a), R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y represents a halogen atom. P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and p + q + r + s = 3.)

M ³ AlR ^c ₄ (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)

R ^d R ^e M ⁴ (B-1c)
(In the general formula (B-1c), R ^d and R ^e 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, and M ⁴ represents Mg. , Zn or Cd.)

  Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.

R ^a _p Al (OR ^b ) _3-p
(In the formula, R ^a and R ^b may be the same or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≦ p ≦ An organoaluminum compound represented by the following formula:

R ^a _p AlY _3-p
(Wherein ^Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number of 0 <p <3). An organoaluminum compound represented,

R ^a _p AlH _3-p
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p <3),

^{_{R a p Al (OR b)}} q Y s
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p represents 0. <P ≦ 3, q is a number of 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as an organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 A tri-branched alkylaluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as 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 Of trialkenylaluminum;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
R ^a _2.5 Al (OR ^b ) _0.5 (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). A partially alkoxylated alkylaluminum having an average composition represented by:
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum 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 ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

A compound similar to (B-1a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded through 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 the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl. Zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like can be mentioned.

  In addition, examples of the organometallic compound (B-1) include 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, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  In addition, a compound capable of forming the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium, is used as the organometallic compound (B-1). It can also be used as

  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) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound (B-2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

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 of allowing water, ice or water vapor 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 unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, the obtained aluminoxane 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 general formula (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, and 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, especially chlorine And hydrocarbon solvents such as bromide and bromide. 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 used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, it is preferably insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound (B-2) used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula (3).

(In the general formula (3), R ¹⁴ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ^{15 s} may be the same as or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number. 1 to 10 hydrocarbon groups are shown.)

  The organoaluminum oxy compound containing boron represented by the general formula (3) is obtained by combining an alkyl boronic acid represented by the following general formula (4) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. Thus, it can be produced by reacting at -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁶ -B (OH) ₂ (4)
(In the general formula (4), R ¹⁶ represents the same group as R ¹⁴ in the general formula (3).)

  Specific examples of the alkyl boronic acid represented by the general formula (4) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluoroboronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. 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 the general formula (B-1a).

  As the organoaluminum compound, 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 above organoaluminum oxy compounds (B-2) are used singly or in combination of two or more.

((B-3) Compound that reacts with transition metal compound (A) to form an ion pair)
As the compound (B-3) (hereinafter referred to as “ionized ionic compound”) that reacts with the transition metal compound (A) to form an ion pair, used in the present invention, JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. 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 used. 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 compounds represented by the following general formula (5).

(In the general formula (5), R ¹⁷ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R ^{18 to} R ^21. May be the same as or different from each other, and are 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-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium 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 ¹⁷ is preferably a carbonium cation or an ammonium cation, 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-ditrifluoromethyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4, Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

  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-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (6) or (7).

(In the formula (6), Et represents an ethyl group.)

(In the formula (7), Et represents an ethyl group.)

Specifically as a borane compound which is an example of an ionized ionic compound (B-3), for example, decaborane (14);
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

  Specific examples of the carborane compound that is an example of the ionized ionic compound (B-3) include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane ( 14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-di Carbanonaborane, 7,8-dicarbaound decaborane (13), 2,7-dicarbaound decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaoundecaborane, dodecahydride- 11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) a Monium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbado Decaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13 ), Tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride- 8-methyl-7,9-dicarbaoundecaborate, (N-Butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n -Butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ) Salts of anions such as ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III ), Tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate Salt (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammo Umbis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) Cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (un Decahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (N-butyl) ammonium] bis (undecahydride-7-carbaundecabo Over G) and salts of the metallic carborane anions such as nickel salt (IV).

  The heteropoly compound which is an example of the ionized ionic compound (B-3) is one or more selected from atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and vanadium, niobium, molybdenum and tungsten. And a compound containing 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, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tungstovanadic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, but not limited thereto. The salt includes, for example, metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. And organic salts such as triphenylethyl salt.

  The isopoly compound which is an example of the ionized ionic compound (B-3) is a compound composed of a metal ion of one kind of atom selected from vanadium, niobium, molybdenum and tungsten, and a molecular ionic species of the metal oxide. Can be considered. Specific examples include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids, but are not limited thereto. The salt includes, for example, metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Examples thereof include organic salts such as salts and triphenylethyl salts.

  The above ionized ionic compounds (compound (B-3) which reacts with the transition metal compound (A) to form an ion pair) are used singly or in combination of two or more.

  In addition to the transition metal compound (A), when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination, the olefin compound exhibits a very high polymerization activity.

  Moreover, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), the organometallic compound (B-1), the organoaluminum oxy compound (B-2), and the ionized ionic compound (B-3). The following carrier (C) may be included as necessary together with at least one compound (B) selected from the group consisting of:

[Carrier (C)]
The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer having a good morphology can be obtained.
As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. can be used, further, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO it can be used, such as ₂ -TiO ₂ -MgO. Among these, as the porous oxide, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferable.

The porous oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _3). ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area. It is desirable that the pore volume be in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume be in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  The clay is usually composed mainly of clay minerals. Moreover, the said ion exchange layered compound is a compound which has a crystal structure where the surface comprised by the ionic bond etc. was piled up in parallel with weak mutual binding force, and the ion to contain is exchangeable. 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, examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.

  Furthermore, as clay and clay minerals, kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite, etc.

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-Ti ( Examples thereof include crystalline acidic salts of polyvalent metals such as NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cc / g and not less than 0.3 to 5 cc / g as measured by mercury porosimetry. It is particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm by mercury porosimetry using a mercury porosimeter.

  When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . 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 guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Can be mentioned. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R represents a hydrocarbon group, etc.) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiO _2, etc. can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  As described above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include a granular or fine particle solid having a particle size in the range of 10 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, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

  The catalyst for olefin polymerization according to the present invention contains the transition metal compound (A), preferably the compound (B), and optionally a carrier (C). An organic compound component (D) can also be included.

[Organic compound component (D)]
In the present invention, the organic compound component (D) improves the polymerization performance (for example, catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the generated polymer (for example, increase the molecular weight of the generated polymer) as necessary. Used for purposes. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and the phenolic compounds, those represented by R ²² —OH are usually used, wherein R ²² is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, carbon atoms). The number is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As the alcohol, R ²² is preferably a halogenated hydrocarbon group. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ²³ —COOH is usually used. R ²³ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

  As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, phosphate having a P═O bond, and a phosphine oxide compound are preferably used.

  As said sulfonate, what is represented by following General formula (8) is mentioned.

(In General Formula (8), M ² is an element of Groups 1 to 14 of the periodic table, and R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated carbonization having 1 to 20 carbon atoms. A hydrogen group, Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7 , U is an integer satisfying 1 ≦ u ≦ 7, and t−u is an integer satisfying t−u ≧ 1.)

<Olefin polymer production method>
The method for producing an olefin polymer of the present invention is a method in which an olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst described above. As described above, the olefin in the present specification refers to a hydrocarbon having one carbon / carbon double bond in the molecule. In the present invention, the copolymerization of olefins may be such that at least one of the monomers is an olefin, and two or more olefins may be copolymerized or a monomer other than the olefin may be copolymerized with the olefin.

The method for using each component constituting the catalyst of the present invention in polymerization and the order of addition to the polymerization vessel are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the transition metal compound (A) alone to the polymerization vessel.
(2) A method of adding the transition metal compound (A) and the compound (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having the transition metal compound (A) supported on the carrier (C) and the compound (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having the compound (B) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C) is added to a polymerization vessel.
(6) A method in which the catalyst component having the transition metal compound (A) and the compound (B) supported on the carrier (C) and the compound (B) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(7) A method in which the catalyst component having the compound (B) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(8) A method in which the catalyst component having the compound (B) supported on the carrier (C), the transition metal compound (A), and the compound (B) are added to the polymerization vessel in an arbitrary order. In this case, the compounds (B) may be the same or different.
(9) A method in which a component carrying the transition metal compound (A) on the carrier (C) and a component carrying the compound (B) on the carrier (C) are added to the polymerization vessel in any order.
(10) A method in which a component in which the transition metal compound (A) is supported on the carrier (C), a component in which the compound (B) is supported on the carrier (C), and the compound (B) are added to an arbitrary sequential polymerization vessel. In this case, the compounds (B) may be the same or different.
(11) A method in which the transition metal compound (A), the compound (B), and the organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(12) A method in which the component (B) and the organic compound component (D) previously contacted and the transition metal compound (A) are added to the polymerization vessel in an arbitrary order.
(13) A method in which the component (B) and the organic compound component (D) supported on the carrier (C) and the transition metal compound (A) are added to the polymerization vessel in any order.
(14) A method in which the catalyst component obtained by previously contacting the transition metal compound (A) and the compound (B) and the organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(15) A method in which the transition metal compound (A) and the compound (B) are contacted in advance, and the compound (B) and the organic compound component (D) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(16) A catalyst component in which the transition metal compound (A) and the compound (B) are contacted in advance, and a component in which the compound (B) and the organic compound component (D) are contacted in advance are added to the polymerization vessel in any order. Method. In this case, the compounds (B) may be the same or different.
(17) A method in which a component in which a transition metal compound (A) is supported on a carrier (C), a compound (B), and an organic compound component (D) are added to the polymerization vessel in an arbitrary order.
(18) A method in which a component in which the transition metal compound (A) is supported on the carrier (C) and a component in which the compound (B) and the organic compound component (D) are contacted in advance are added to the polymerization vessel in any order.
(19) A method in which a catalyst component obtained by bringing a transition metal compound (A), a compound (B) and an organic compound component (D) into contact in advance in an arbitrary order is added to a polymerization vessel.
(20) A method in which a transition metal compound (A), a compound (B) and an organic compound component (D) are contacted in advance in any order, and the compound (B) is added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.
(21) A method in which a catalyst in which a transition metal compound (A), a compound (B), and an organic compound component (D) are supported on a carrier (C) is added to a polymerization vessel.
(22) A method in which the transition metal compound (A), the compound (B), the catalyst component having the organic compound component (D) supported on the carrier (C), and the compound (B) are added to the polymerization vessel in any order. In this case, the compounds (B) may be the same or different.

  The solid catalyst component in which the transition metal compound (A) is supported on the carrier (C) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the carrier (C) are preliminarily provided with olefin. It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

  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. 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, and methylcyclopentane. Alicyclic hydrocarbons such as: aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, and (co) polymerization The olefin (monomer) to be provided can also be used as a solvent.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻¹⁰ per liter of reaction volume. It is used in such an amount that it becomes ^-3 mol.

  The organometallic compound (B-1) usually has a molar ratio [(B-1) / M] of the organometallic compound (B-1) and all transition metal atoms (M) in the transition metal compound (A). It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is a molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) [(B-2). / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. The compound that reacts with the transition metal compound (A) to form an ion pair (ionized ionic compound) (B-3) includes the ionized ionic compound (B-3) and the transition metal in the transition metal compound (A). The molar ratio [(B-3) / M] with the atom (M) is usually 1 to 10, preferably 1 to 5.

  When the compound (B) is an organometallic compound (B-1), the organic compound component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0. Used in such an amount that it becomes 1-5. When the compound (B) is an organoaluminum oxy compound (B-2), the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. Used in various amounts. When the compound (B) is an ionized ionic compound (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Used in quantity.

Moreover, the polymerization temperature of the olefin using such an olefin 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 -G, preferably from normal pressure to 50 kg / cm ² -G, and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can also be done. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the compound (B) to be used.

  The olefin that can be polymerized by such an olefin polymerization catalyst of the present invention is not particularly limited, but a linear or branched α-olefin having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, For example, ethylene, propylene, 1-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-eicocene; cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene Tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8 - such octahydronaphthalene and the like.

  The olefin polymerization catalyst of the present invention can also copolymerize olefins and other monomers. The other monomer may be any monomer other than olefin, and is not particularly limited. For example, a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.) and a polymerizable carbon / carbon double bond are included in the molecule. Monomer (hereinafter also referred to as polar group-containing monomer).

Specific examples of the polar group-containing monomer include acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid. 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid 20-Henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, 3-vinyl Benzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, -(10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.2.1] -5-heptene-2,3- Unsaturated carboxylic acids such as dicarboxylic acids, and metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, and calcium salts, and methyl esters, ethyl esters, and n-propyls of these unsaturated carboxylic acids Unsaturated carboxylic acid esters such as ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester (in the case where the unsaturated carboxylic acid is a dicarboxylic acid, Can also be diesters), and amides of these unsaturated carboxylic acids, N, N-di- Unsaturated carboxylic acid amides such as Chiruamido (may be a diamide be a monoamide when unsaturated carboxylic acid is a dicarboxylic acid);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1 ] Unsaturated carboxylic acid anhydrides such as -5-heptene-2,3-dicarboxylic acid anhydride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
Silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane;
Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5-heptene;
Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol And unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates, stearates;
Substituted phenols such as vinylphenol and allylphenol;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, allyl anisole;
Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl-7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;
Unsaturated sulfoxides such as allyl phenyl sulfoxide;
Unsaturated sulfones such as allyl phenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
And unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

  Furthermore, examples of the polar group-containing monomer include vinyl benzyl acetate, hydroxystyrene, methyl 4- (3-butenyloxy) benzoate, methoxystyrene, ethoxystyrene, allyl trifluoroacetate, o-chlorostyrene, and p-chlorostyrene. Glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholine, allyl glycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytrifluoro Rushiran etc. also mentioned, it is possible to olefin copolymerized with the olefin polymerization catalyst of the present invention.

  Moreover, as a monomer other than the polar group-containing monomer, vinylcyclohexane, diene, polyene, or the like can be used. In the presence of the olefin polymerization catalyst of the present invention, these monomers can also be copolymerized with the olefin.

  Examples of the diene or polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and having two or more carbon / carbon double bonds. Specifically, 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, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, divinylbenzene; 7-methyl-1,6- Examples include octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.

Furthermore, an aromatic vinyl compound can be used as another monomer. Specifically, mono- or polyalkyl styrene such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene; and 3-phenylpropylene, 4-phenylpropylene , Α-methylstyrene and the like.
As described above, the olefin polymerization catalyst of the present invention can produce a polymer with high polymerization activity.

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

The structures of the compounds obtained in the synthesis examples and the examples are 270 MHz ¹ H NMR (manufactured by JEOL Ltd., apparatus name GSH-270), GC-MS (manufactured by Shimadzu Corporation, apparatus name QP2010 Ultra), FD-mass spectrometry (Japan) It was determined using an electronic product, device name SX-102A) or the like.

  The intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

(1) Synthesis of ligand [Synthesis Example 1]
A 200 mL reactor thoroughly dried and purged with nitrogen was charged with 65 mL of acetic acid, 12.1 g (50 mmol) of 2-adamantyl-4-methylphenol, and 67 mL of dichloromethane, and then 3.2 mL (62 mmol) of bromine under ice cooling. added. After stirring at room temperature for 3 hours, the reaction solution was dropped into 100 mL of a saturated aqueous sodium nitrite solution to quench the reaction. Soluble components were extracted with dichloromethane, and the obtained fractions were washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain 15.4 g (yield 96%) of the desired product represented by the following formula [1] (hereinafter referred to as compound [1]).

GC-mass spectrometry (M ^<+> ): 320
¹ H-NMR (270 MHz, CDCl ₃ ): 7.15 (1H, d, J = 1.8 Hz), 6.98 (1H, d, J = 1.8 Hz), 5.62 (1H, s), 2.25 (3H, s), 2.10 (9H, s), 1.77 (6H, s) ppm

[Synthesis Example 2]
In a 300 mL reactor thoroughly dried and purged with nitrogen, 12.9 g (40.0 mmol) of compound [1] and 60 mL of tetrahydrofuran were charged and cooled to 0 ° C. 1.76 g (60 wt%, 44.1 mmol) of sodium hydride (oil) was added and stirred at 0 ° C. for 1 hour, and then 3.6 mL (47.4 mmol) of chloromethyl methyl ether was added at 0 ° C. After stirring at room temperature for 17 hours, the reaction was quenched by adding water little by little under ice cooling. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain 14.4 g (yield 99%) of the desired product (hereinafter referred to as compound [2]) represented by the following formula [2].

GC-mass spectrometry (M ^<+> ): 364
¹ H-NMR (270 MHz, CDCl ₃ ): 7.23 (1H, d, J = 1.8 Hz), 7.03 (1H, d, J = 1.8 Hz), 5.21 (2H, s), 3.70 (3H, s), 2.27 (3H, s), 2.10 (9H, s), 1.77 (6H, s) ppm

[Synthesis Example 3]
A 500 mL reactor sufficiently dried and purged with nitrogen was charged with 5.2 mL (47.8 mmol) of anisole, 7.2 mL (48.3 mmol) of tetramethylethylenediamine and 110 mL of diethyl ether, and cooled to -78 ° C. After adding 30 mL (48.0 mmol) of normal butyl lithium hexane solution and stirring at −78 ° C. for 1 hour, the mixture was stirred at room temperature. After 1 hour and 30 minutes, the mixture was cooled again to −78 ° C., 5.4 mL (48.4 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 15 hours and 30 minutes, the reaction solution was evaporated under reduced pressure and sufficiently dried under reduced pressure to obtain a white solid. Compound [2] 14.4 g (40.1 mmol), palladium acetate 0.45 g (2.00 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 1.65 g (4.01 mmol), 25.5 g (120.3 mmol) of potassium phosphate, 68 mL of tetrahydrofuran, and 17 mL of water were charged and heated in an oil bath at 60 ° C. for 3 hours. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and the target product (hereinafter referred to as compound [3]) represented by the following formula [3] was 5 .87 g (yield 37%) was obtained.

GC-mass spectrometry (M ^<+> ): 392
¹ H-NMR (270 MHz, CDCl ₃ ): 7.33 (1H, dd, J = 8.0, 1.5 Hz), 7.27 (1H, dd, J = 7.0, 1.4 Hz), 7 .09 (1H, d, J = 1.1 Hz), 7.00 (1H, dd, J = 7.0, 1.1 Hz), 6.97 (1H, d, J = 8.1 Hz), 6. 92 (1H, d, J = 1.6 Hz), 4.45 (2H, s), 3.80 (3H, s), 3.21 (3H, s), 2.31 (3H, s), 2 .17 (6H, s), 2.09 (3H, s), 1.78 (6H, s) ppm

[Synthesis Example 4]
In a 200 mL reactor thoroughly dried and purged with nitrogen, 4.56 g (11.6 mmol) of Compound [3], 2.1 mL (14.1 mmol) of tetramethylethylenediamine, 30 mL of diethyl ether, and 5 mL of tetrahydrofuran were charged, and -78 ° C. Cooled to. 8.7 mL (13.9 mmol) of normal butyl lithium hexane solution was added and stirred at −78 ° C. for 1 hour and then at room temperature. After 1 hour, the mixture was again cooled to −78 ° C., 3.93 g (15.5 mmol) of iodine dissolved in 25 mL of tetrahydrofuran was added, and the mixture was stirred while gradually warming to room temperature. After 15 hours, the reaction solution was added dropwise to 100 mL of a saturated aqueous sodium sulfite solution to quench the reaction. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent from the filtrate under reduced pressure was purified by silica gel column chromatography, and the desired product (hereinafter referred to as compound [4]) represented by the following formula [4] was 1 .49 g (28% yield) was obtained.

GC-mass spectrometry (M ^<+> ): 518
¹ H-NMR (270 MHz, CDCl ₃ ): 7.77 (1H, dd, J = 8.1, 1.6 Hz), 7.34 (1H, dd, J = 7.6, 1.6 Hz), 7 .12 (1H, d, J = 2.4 Hz), 6.98 (1H, d, J = 2.4 Hz), 6.88 (1H, t, J = 7.6 Hz), 4.50 (2H, s), 3.45 (3H, s), 3.21 (3H, s), 2.32 (3H, s), 2.15 (6H, s), 2.09 (3H, s), 1. 78 (6H, s) ppm

[Synthesis Example 5]
In a 100 mL reactor thoroughly dried and purged with nitrogen, 1.10 g (4.56 mmol) of 2-adamantyl-4-methylphenol and 6.8 mL of tetrahydrofuran were charged and cooled to 0 ° C. Sodium hydride (oil) 0.26 g (60 wt%, 6.45 mmol) was added and stirred at 0 ° C. for 40 minutes, then at room temperature for 2 hours, and then cooled to 0 ° C. again. Chloromethyl methyl ether 0.5 mL (6.58 mmol) was added at 0 ° C., and the mixture was stirred while gradually warming to room temperature. After 16 hours and 30 minutes, the reaction was quenched by adding water little by little under ice cooling. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure, and it was sufficiently dried under reduced pressure to obtain a yellow oily substance. This was dissolved in 10 mL of diethyl ether, added with 3.4 mL (5.58 mmol) of normal butyl lithium hexane solution at room temperature, and stirred at room temperature. After 2 hours, the mixture was cooled to −78 ° C., 0.6 mL (5.38 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 16 hours, the reaction solution was evaporated under reduced pressure and sufficiently dried under reduced pressure to obtain a white solid. To this, compound [4] 1.64 g (3.17 mmol), palladium acetate 35.7 mg (0.16 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 0.13 g (0.32 mmol), 2.02 g (9.53 mmol) of potassium phosphate, 5.2 mL of tetrahydrofuran, and 1.3 mL of water were charged, and heated in an oil bath at 60 ° C. for 6 hours. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and the target product represented by the following formula [5] (hereinafter referred to as compound [5]) was 0. .48 g (22% yield) was obtained.

FD-mass spectrometry (M ⁺ ): 676

[Synthesis Example 6]
In a well-dried 50 mL reactor, 0.47 g (0.70 mmol) of compound [5], 0.80 g (4.22 mmol) of paratoluenesulfonic acid monohydrate, 5 mL of ethanol, and 6.5 mL of dichloromethane were charged. After stirring for 20 hours at room temperature, the mixture was stirred for 5 hours at 50 ° C. in an oil bath. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The mixture was diluted with dichloromethane, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain 0.39 g (yield 94%) of the desired product (hereinafter referred to as compound (6)) represented by the following formula (6).

FD-mass spectrometry (M ⁺ ): 588
¹ H-NMR (270 MHz, CDCl ₃ ): 7.40-7.29 (3H, m), 7.09 (2H, d, J = 1.4 Hz), 6.95 (2H, d, J = 1) .4 Hz), 6.05 (2H, s), 3.34 (3H, s), 2.33 (6H, s), 2.19 (12H, s), 2.08 (6H, s), 1 .79 (12H, s) ppm

[Synthesis Example 7]
A 300 mL reactor sufficiently dried and purged with nitrogen was charged with 8.50 g (49.9 mmol) of 2-phenylphenol and 75 mL of tetrahydrofuran, and cooled to 0 ° C. 2.82 g (60 wt%, 70.5 mmol) of sodium hydride (oil) was added and stirred at 0 ° C. for 1 hour, and then stirred at room temperature for 3 hours. Then, it cooled to 0 degreeC and 5.2 mL (68.5 mmol) of chloromethyl methyl ether was added at 0 degreeC. After stirring at room temperature for 16 hours, the reaction was quenched by adding water little by little under ice cooling. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain a light brown oily substance. This was dissolved in 110 mL of diethyl ether, 37 mL (59.8 mmol) of a normal butyl lithium hexane solution was added at room temperature, and the mixture was stirred at room temperature. After 4 hours, the mixture was cooled to −78 ° C., 6.8 mL (61.0 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 16 hours, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was sufficiently dried under reduced pressure to obtain a pale yellow solid. To this, 10.4 g (44.5 mmol) of 2-iodoanisole, 0.50 g (2.23 mmol) of palladium acetate, 1.25 g (3.06 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, 28.3 g (133.4 mmol) of potassium phosphate, 76 mL of tetrahydrofuran, and 19 mL of water were charged and heated in an oil bath at 60 ° C. for 4 hours. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was evaporated under reduced pressure to give a brown solid. This solid was dissolved in 95 mL of diethyl ether, charged into a 500 mL reactor thoroughly dried and purged with nitrogen, and then 8.0 mL (53.7 mmol) of tetramethylethylenediamine was added and cooled to -78 ° C. After adding 32 mL (52.5 mmol) of normal butyl lithium hexane solution and stirring at -78 ° C for 2 hours, the mixture was stirred at room temperature for 2 hours. Then, it cooled to -78 degreeC, the iodine 15.8g (62.3 mmol) dissolved in tetrahydrofuran 85mL was added, and it stirred, heating up gradually to room temperature. After 16 hours, the reaction solution was added dropwise to 200 mL of a saturated aqueous sodium sulfite solution to quench the reaction. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and the target product represented by the following formula [7] (hereinafter referred to as compound [7]) was 8 .44 g (42% yield) was obtained.

GC-mass spectrometry (M ^<+> ): 446
¹ H-NMR (270 MHz, CDCl ₃ ): 7.79 (1H, dd, J = 7.8, 1.6 Hz), 7.62-7.58 (2H, m), 7.45-7.32 (5H, m), 7.25 (1H, t, J = 4.1 Hz), 6.91 (1H, t, J = 7.8 Hz), 4.37 (2H, s), 3.54 (3H , S), 2.62 (3H, s) ppm

[Synthesis Example 8]
2-phenylphenol 5.11 g (30.0 mmol) and tetrahydrofuran 45 mL were charged into a 200 mL reactor sufficiently dried and purged with nitrogen, and cooled to 0 ° C. 1.68 g (60 wt%, 42.0 mmol) of sodium hydride (oil) was added and stirred at 0 ° C. for 1 hour, and then stirred at room temperature for 2 hours and 30 minutes. Then, it cooled to 0 degreeC and 3.2 mL (42.1 mmol) of chloromethyl methyl ether was added at 0 degreeC. After stirring at room temperature for 17 hours, the reaction was quenched by adding water little by little under ice cooling. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was evaporated under reduced pressure to obtain 6.92 g of a light brown oily substance. 4.86 g of this oily substance was dissolved in 50 mL of diethyl ether, 16.5 mL (27.1 mmol) of normal butyl lithium hexane solution was added at room temperature, and the mixture was stirred at room temperature. After 2 hours, the mixture was cooled to −78 ° C., 3.0 mL (26.9 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 16 hours, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was sufficiently dried under reduced pressure to obtain a pale yellow solid. To this, 8.44 g (18.9 mmol) of compound (7), 0.21 g (0.94 mmol) of palladium acetate, 0.78 g (1.89 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, Charged 12.1 g (57.2 mmol) of potassium phosphate, 32 mL of tetrahydrofuran, and 8 mL of water, and heated in an oil bath at 60 ° C. for 4 hours. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and the target product represented by the following formula [8] (hereinafter referred to as compound [8]) was 8 .67 g (yield 86%) was obtained.

¹ H-NMR (270 MHz, CDCl ₃ ): 7.61 (4H, dd, J = 8.4, 1.4 Hz), 7.43 (4H, d, J = 7.6 Hz), 7.40 (4H , Dd, J = 7.6, 1.9 Hz), 7.35 (2H, d, J = 2.2 Hz), 7.33-7.31 (1H, m), 7.27-7.20 ( 4H, m), 4.43 (4H, s), 3.44 (3H, s), 2.71 (6H, s) ppm

[Synthesis Example 9]
A fully dry 500 mL reactor was charged with 8.66 g (16.3 mmol) of compound [8], 18.6 g (97.8 mmol) of paratoluenesulfonic acid monohydrate, 115 mL of ethanol, and 75 mL of dichloromethane at room temperature. After stirring for 16 hours, the mixture was stirred at 50 ° C. for 2 hours. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The mixture was diluted with dichloromethane, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain 7.93 g of the desired product represented by the following formula [9] (hereinafter referred to as compound [9]).

GC-mass spectrometry (M ^<+> ): 444
¹ H-NMR (270 MHz, CDCl ₃ ): 7.58 (4H, dd, J = 8.2, 1.4 Hz), 7.46 (4H, dd, J = 6.9, 1.8 Hz), 7 .43 (2H, d, J = 1.6 Hz), 7.40-7.33 (7H, m), 7.09 (2H, t, J = 7.6 Hz), 6.34 (2H, s) , 3.40 (3H, s) ppm

[Synthesis Example 10]
A well-dried, nitrogen-substituted 300 mL reactor was charged with 2.81 g (60 wt%, 70.2 mmol) of sodium hydride (oil) and 50 mL of tetrahydrofuran and cooled to 0 ° C. 7.51 g (50.0 mmol) of 4-tert-butylphenol dissolved in 25 mL of tetrahydrofuran was dropped into the reactor at 0 ° C., stirred at 0 ° C. for 1 hour, and then stirred at room temperature for 2 hours. Then, it cooled to 0 degreeC and 5.2 mL (68.5 mmol) of chloromethyl methyl ether was added at 0 degreeC. After stirring at room temperature for 16 hours, the reaction was quenched by adding water little by little under ice cooling. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain a pale yellow oily substance. This oily substance was dissolved in 110 mL of diethyl ether, and 36 mL (59.0 mmol) of a normal butyl lithium hexane solution was added at room temperature, followed by stirring at room temperature. After 3 hours, the mixture was cooled to −78 ° C., 6.8 mL (61.0 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 15 hours and 30 minutes, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was sufficiently dried under reduced pressure to obtain a pale yellow solid. To this, 13.5 g (50.0 mmol) of 1-bromo-2,4-di-tert-butylbenzene, 0.56 g (2.51 mmol) of palladium acetate, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxy Biphenyl (2.05 g, 4.99 mmol), potassium phosphate (31.8 g, 149.9 mmol), tetrahydrofuran (80 mL) and water (20 mL) were charged, and the mixture was heated in an oil bath at 60 ° C. for 4 hours and 30 minutes. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure is purified by silica gel column chromatography, and contains the desired product (hereinafter referred to as compound [10]) represented by the following formula [10]. 12.0 g (purity 93%, yield 58%) of a yellow oily substance was obtained.

GC-mass spectrometry (M ^<+> ): 382

[Synthesis Example 11]
In a 200 mL reactor thoroughly dried and purged with nitrogen, 7.57 g (18.5 mmol) of compound [10] and 43 mL of diethyl ether were charged, and 14.5 mL (23.8 mmol) of normal butyl lithium hexane solution was added at room temperature. And stirred at room temperature for 2 hours. Thereafter, the mixture was cooled to −78 ° C., 2.7 mL (24.2 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 15 hours and 30 minutes, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was sufficiently dried under reduced pressure to obtain a pale yellow solid. To this, 4.63 g (19.8 mmol) of 2-iodoanisole, 0.22 g (0.99 mmol) of palladium acetate, 0.81 g (1.98 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, 12.6 g (59.4 mmol) of potassium phosphate, 32 mL of tetrahydrofuran, and 8 mL of water were charged, and heated in an oil bath at 60 ° C. for 4 hours and 30 minutes. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography, and the desired product (hereinafter referred to as compound [11]) represented by the following formula [11] was 5 .70 g (yield 63%) was obtained.

GC-mass spectrometry (M ^<+> ): 488
¹ H-NMR (270 MHz, CDCl ₃ ): 7.42 (2H, d, J = 1.9 Hz), 7.40-7.29 (5H, m), 7.05-6.98 (2H, m ), 4.29 (2H, s), 3.83 (3H, s), 2.55 (3H, s), 1.36 (18H, s), 1.35 (9H, s) ppm

[Synthesis Example 12]
In a 200 mL reactor thoroughly dried and purged with nitrogen, 5.69 g (11.6 mmol) of compound [11], 2.1 mL (14.1 mmol) of tetramethylethylenediamine and 25 mL of diethyl ether were charged and cooled to -78 ° C. . After adding 8.5 mL (13.9 mmol) of normal butyllithium hexane solution and stirring at −78 ° C. for 1 hour and 30 minutes, the mixture was stirred at room temperature for 3 hours. Thereafter, the mixture was cooled to −78 ° C., 4.16 g (16.4 mmol) of iodine dissolved in 23 mL of tetrahydrofuran was added, and the mixture was stirred while gradually warming to room temperature. After 21 hours, the reaction solution was added dropwise to 50 mL of a saturated aqueous sodium sulfite solution to quench the reaction. Soluble fractions were extracted with ethyl acetate, and the obtained fractions were washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the residue obtained by evaporating the solvent from the filtrate under reduced pressure was purified by silica gel column chromatography to obtain 5% of the desired product (hereinafter referred to as compound [12]) represented by the following formula [12]. .16 g (yield 72%) was obtained.

GC-mass spectrometry (M ^<+> ): 614
¹ H-NMR (270 MHz, CDCl ₃ ): 7.77 (1H, dd, J = 7.8, 1.6 Hz), 7.50 (1H, dd, J = 7.8, 1.6 Hz), 7 .41 (2H, t, J = 1.2 Hz), 7.40-7.37 (3H, m), 6.90 (1H, t, J = 7.8 Hz), 4.33 (2H, s) , 3.56 (3H, s), 2.60 (3H, s), 1.37 (18H, s), 1.35 (9H, s) ppm

[Synthesis Example 13]
In a 100 mL reactor thoroughly dried and purged with nitrogen, 4.18 g (10.2 mmol) of compound [10] and 24 mL of diethyl ether were charged, and 8.0 mL (13.1 mmol) of normal butyl lithium hexane solution was added at room temperature. The mixture was stirred at room temperature for 3 hours and 30 minutes. Thereafter, the mixture was cooled to −78 ° C., 1.5 mL (13.5 mmol) of trimethoxyborane was added, and the mixture was stirred while gradually warming to room temperature. After 16 hours, the solvent of the reaction solution was distilled off under reduced pressure, and the residue was sufficiently dried under reduced pressure to obtain a pale yellow solid. To this, 5.14 g (8.37 mmol) of compound [12], 0.096 g (0.43 mmol) of palladium acetate, 0.35 g (0.85 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, A solution containing 5.34 g (25.2 mmol) of potassium phosphate, 14 mL of tetrahydrofuran, and 3.5 mL of water was heated in an oil bath at 60 ° C. for 4 hours. The reaction mixture was cooled to room temperature, ethyl acetate was added, and the mixture was filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, 13 mL of ethyl acetate was added to the residue obtained by distilling off the solvent under reduced pressure. The pale yellow suspension obtained here was filtered, and the obtained solid was sufficiently dried under reduced pressure to obtain 3.78 g of the desired product represented by the following formula [13] (hereinafter referred to as compound [13]). Yield 52%).

¹ H-NMR (270 MHz, CDCl ₃ ): 7.48 (2H, d, J = 7.6 Hz), 7.43 (4H, d, J = 1.8 Hz), 7.41 (2H, d, J = 2.7 Hz), 7.39 (2 H, d, J = 1.8 Hz), 7.37 (2 H, d, J = 2.7 Hz), 7.20 (1 H, t, J = 7.6 Hz) , 4.40 (4H, s), 3.54 (3H, s), 2.65 (6H, s), 1.36 (36H, s), 1.36 (18H, s) ppm.

[Synthesis Example 14]
A sufficiently dry 200 mL reactor was charged with 3.77 g (4.34 mmol) of compound [13], 4.95 g (26.0 mmol) of paratoluenesulfonic acid monohydrate, 30 mL of ethanol, and 18 mL of dichloromethane at room temperature. After stirring for 18 hours, the mixture was stirred at 50 ° C. for 4 hours. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. The mixture was diluted with dichloromethane, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the solvent of the filtrate was distilled off under reduced pressure to obtain 3.48 g of the desired product represented by the following formula [14] (hereinafter referred to as compound [14]).

FD-mass spectrometry (M ⁺ ): 781
¹ H-NMR (270 MHz, CDCl ₃ ): 7.48 (2H, d, J = 7.8 Hz), 7.44 (2H, t, J = 1.9 Hz), 7.39 (4H, d, J = 1.9 Hz), 7.37-7.34 (5H, m), 6.18 (2H, s), 3.42 (3H, s), 1.36 (54H, s) ppm

(2) Synthesis of transition metal compound [Example 1]
In a 100 mL reactor thoroughly dried and purged with argon, 0.29 g (0.49 mmol) of compound [6] and 5 mL of tetrahydrofuran were charged, cooled to −78 ° C., and stirred. To this was added 0.60 mL of n-butyllithium (n-hexane solution, 1.64 M, 0.98 mmol), and the mixture was stirred at the same temperature for 1 hour, slowly returned to room temperature, and further stirred for 2 hours to obtain a lithium salt. Adjusted. This solution was added dropwise to 5 mL of a tetrahydrofuran solution containing 0.18 g (0.49 mmol) of zirconium tetrachloride tetrahydrofuran complex cooled to −78 ° C. After completion of dropping, stirring was continued for 18 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 20 mL of methylene chloride, and insoluble matters were removed with a glass filter. 15 mL of n-hexane was added to the filtrate and stirred, the solution was concentrated about half and the precipitated solid was filtered off with a glass filter and dried under reduced pressure to give a white powder compound represented by the following formula [A] (hereinafter referred to as zirconium). 0.10 g (yield 25%) of compound [A] was obtained.

FD-mass spectrometry (M ⁺ -THF): 746

[Example 2]
In a 100 mL reactor sufficiently dried and purged with argon, 0.66 g (1.49 mmol) of compound [9] and 15 mL of tetrahydrofuran were charged, cooled to -78 ° C, and stirred. To this was added 1.81 mL of n-butyllithium (n-hexane solution, 1.64 M, 2.97 mmol), and the mixture was stirred at the same temperature for 1 hour, then slowly returned to room temperature, and further stirred for 1 hour to obtain a lithium salt. Adjusted. This solution was added dropwise to 15 mL of a tetrahydrofuran solution containing 0.56 g (1.48 mmol) of zirconium tetrachloride tetrahydrofuran complex cooled to −78 ° C. After completion of dropping, stirring was continued for 18 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 mL of methylene chloride, and insoluble matters were removed with a glass filter. 20 mL of n-hexane was added to the filtrate and stirred, the solution was concentrated about half, and the precipitated solid was filtered off with a glass filter and dried under reduced pressure to give a white powder compound represented by the following formula [B] (hereinafter referred to as zirconium). 0.64 g (yield 64%) of compound [B] was obtained.

FD-mass spectrometry (M ⁺ -THF): 602

[Example 3]
In a 100 mL reactor sufficiently dried and purged with argon, 1.28 g (1.63 mmol) of compound [14] and 15 mL of tetrahydrofuran were charged, cooled to −78 ° C., and stirred. To this was added 2.00 mL of n-butyllithium (n-hexane solution, 1.64 M, 3.28 mmol), and the mixture was stirred at the same temperature for 1 hour, slowly returned to room temperature, and further stirred for 2 hours to obtain a lithium salt. Adjusted. This solution was added dropwise to 15 mL of a tetrahydrofuran solution containing 0.62 g (1.63 mmol) of zirconium tetrachloride tetrahydrofuran complex cooled to −78 ° C. After completion of dropping, stirring was continued for 18 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 mL of methylene chloride, and insoluble matters were removed with a glass filter. 25 mL of n-hexane was added to the filtrate and stirred, the solution was concentrated about half, and the precipitated solid was filtered off with a glass filter and dried under reduced pressure to give a white powder compound represented by the following formula [C] (hereinafter referred to as zirconium). 0.69 g (yield 42%) of compound [C] was obtained.

FD-mass spectrometry (M ⁺ -THF): 939

[Example 4]
In a 100 mL reactor sufficiently dried and purged with argon, 1.25 g (1.60 mmol) of compound [14] and 15 mL of diethyl ether were charged, cooled to −78 ° C., and stirred. To this was added 1.95 mL of n-butyllithium (n-hexane solution, 1.64 M, 3.20 mmol), and the mixture was stirred at the same temperature for 1 hour, slowly returned to room temperature, and further stirred for 2 hours to obtain a lithium salt. Adjusted. This solution was added dropwise to 15 mL of a diethyl ether solution containing 0.37 g (1.60 mmol) of zirconium tetrachloride cooled to −78 ° C. After completion of dropping, stirring was continued for 18 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 mL of methylene chloride, and insoluble matters were removed with a glass filter. 25 mL of n-hexane was added to the filtrate and stirred, and the solution was concentrated about half. The precipitated solid was filtered off with a glass filter and dried under reduced pressure to give a white powder compound represented by the following formula [D] (hereinafter referred to as zirconium). 0.68 g (yield 45%) of compound [D] was obtained.

FD-mass spectrometry (M ⁺ ): 939

[Example 5]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with 100 liters / hr of ethylene. Thereafter, 0.125 mmol of triisobutylaluminum (TIBA), 0.005 mmol of the zirconium compound (A) obtained in Example 1, and 0.0075 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). In addition, polymerization was started. Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 50 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

  After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.22 g of polyethylene. The polymerization activity was 264 kg / mol-Zr · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 3.15 dL / g.

[Example 6]
Ethylene polymerization was carried out in the same manner as in Example 5 except that the polymerization temperature was 75 ° C., and 0.42 g of polyethylene was obtained. The polymerization activity was 504 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.14 dL / g.

[Example 7]
Ethylene polymerization was carried out in the same manner as in Example 5 except that the polymerization temperature was 95 ° C., and 0.53 g of polyethylene was obtained. The polymerization activity was 636 k / mol-Zr · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 2.09 dL / g.

[Example 8]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Thereafter, 0.125 mmol of triisobutylaluminum (TIBA), 0.005 mmol of the zirconium compound (B) obtained in Example 2, and 0.0075 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB). In addition, polymerization was started. Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 50 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

  After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.13 g of polyethylene. The polymerization activity was 156 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.35 dL / g.

[Example 9]
Ethylene polymerization was carried out in the same manner as in Example 8 except that the polymerization temperature was 75 ° C., and 0.35 g of polyethylene was obtained. The polymerization activity was 420 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.15 dL / g.

[Example 10]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Thereafter, 0.125 mmol of triisobutylaluminum (TIBA), 0.005 mmol of zirconium compound (C) obtained in Example 3, and 0.0075 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were obtained. In addition, polymerization was started. Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 50 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

  After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.20 g of polyethylene. The polymerization activity was 240 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.85 dL / g.

[Example 11]
Ethylene polymerization was carried out in the same manner as in Example 10 except that the polymerization temperature was 75 ° C., and 0.40 g of polyethylene was obtained. The polymerization activity was 480 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.09 dL / g.

[Example 12]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Thereafter, 0.125 mmol of triisobutylaluminum (TIBA), 0.005 mmol of the zirconium compound (D) obtained in Example 4, and 0.0075 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were obtained. In addition, polymerization was started. Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 50 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

  After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.22 g of polyethylene. The polymerization activity was 264 kg / mol-Zr · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 2.81 dL / g.

  Since the catalyst for olefin polymerization containing the novel transition metal compound according to the present invention exhibits high olefin polymerization activity, the present invention is industrially extremely valuable.

Claims (7)

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

(In General Formula (1), M represents a transition metal atom in Groups 3 to 10 of the periodic table.
R ^{1 to} R ³ may be the same as or different from each other, and are 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ^{1 to} R ³ may be connected to each other to form a ring, and the ring is further substituted It may have a group.
C ¹ and C ² represent carbon atoms.
D is an oxygen atom having one substituent R ⁴ (structure represented by OR ⁴ ), a sulfur atom having one substituent R ⁴ (structure represented by SR ⁴ ), and two substituents R ⁴ nitrogen atom having ^{(N (structure} represented by R _{4) 2),} or represents the substituent ^{R 4} two having phosphorus atom ^{(P (structure} represented by R _{4) 2),} ^{R 4} is hydrogen Indicates an atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group When a plurality of R ⁴ are present, they may be the same or different from each other, and two or more may be connected to each other to form a ring, and the ring may further have the above substituents. .
L ¹ and L ² may be the same or different from each other, and an oxygen atom, a sulfur atom, a nitrogen atom having a substituent R ⁵ (structure represented by NR ⁵ ), or a phosphorus atom having a substituent R ⁵ (Structure represented by PR ⁵ ) wherein R ⁵ is 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
E ¹ and E ² may be the same or different from each other, and each represents a linking group containing at least one carbon atom, silicon atom or germanium atom connecting C ¹ and L ¹ , C ² and L ² , The group may further have a substituent included in the definition of R ^{1 to} R ⁵ .
n represents the valence of M.
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when a plurality of Xs are present, they may be the same as or different from each other, and two or more may be linked to each other to form a ring. ) The transition metal compound according to claim 1, wherein C ¹ -E ¹ -L ¹ and C ² -E ² -L ² in the general formula (1) form a structure represented by the following general formula (2). A).

(In the general formula (2), Q ¹ and Q 2 may be the same as or different from each other, and represent a carbon atom, a silicon atom, or a germanium atom.
y is the number of Q ¹ and z is the number of Q ² , which may be the same as or different from each other, and represents 0 or an integer of 1 to 5. When y and z are 0, C ¹ and C ² and the benzene ring are directly bonded. When y and z are integers of 2 to 5, a plurality of adjacent Q ¹ and Q ² are bonded to each other to form a single bond or a double bond. In the case of forming a double bond, there is no substituent of A ² or A ⁴ in Q ¹ or Q ² forming the double bond.
R ^{6 to} R ¹³ may be the same as or different from each other, and are 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, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them may be connected to each other to form a ring, and the ring further has the above substituents May be.
When y and z are 1 to 5, that is, when Q ¹ and Q ² are present, A ^{1 to} A ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic group. Indicates a compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these are linked to each other May form a ring, and the ring may further have the above substituent. )   The transition metal compound (A) according to claim 2, wherein y and z are 0 or 1.   The transition metal compound (A) according to any one of claims 1 to 3, wherein M is a transition metal atom of Group 4 of the periodic table and n is 4.   The catalyst for olefin polymerization containing the transition metal compound (A) in any one of Claims 1-4. In addition to the transition metal compound (A),
(B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and
(B-3) a compound that reacts with the transition metal compound (A) to form an ion pair,
The olefin polymerization catalyst according to claim 5, comprising at least one compound selected from the group consisting of:   A method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst according to claim 5.