JP2006206500A - Specific transition metal compound, olefin polymerization catalyst comprising the compound and method for polymerizing olefin using the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transition metal compound for polymerization catalyst excellent in olefin polymerization performance. <P>SOLUTION: The new transition metal compound has a structure expressed by general formula (1) [in the general formula, L is expressed by general formula (2), wherein R<SP>1</SP>to R<SP>4</SP>express each H, a halogen atom, a hydrocarbon group or the like; R<SP>5</SP>and R<SP>6</SP>express each the atom or the group same as those of R<SP>1</SP>to R<SP>4</SP>; Q expresses a tetracordinated boron, aluminum or the like; D expresses a group expressed by general formula (3) which coordinates to M through V which expresses carbene or a hetero atom: V expresses carbene, N, O, S or P; R<SP>a</SP>and R<SP>b</SP>express a 1-20C hydrocarbon group; M expresses a transition metal atom selected from the 4th-6th family of the periodic table; X expresses H, a halogen atom or a hydrocarbon group; Y expresses a neutral ligand having an electron donating group; m expresses a number satisfying the valency of M; n expresses 0-3 integer]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst comprising a novel transition metal compound and an olefin polymerization method using the olefin polymerization catalyst.

  As the olefin polymerization catalyst, a transition metal compound using a cyclopentadienyl group as a ligand, that is, a Kaminsky catalyst using a so-called metallocene as a part of a catalyst component is well known. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. As the metallocene used in such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Laid-Open No. 58-19309) is used as a non-bridged metallocene, while ethylenebis ( 4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) is known.

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

Therefore, the appearance of a catalyst component for olefin polymerization excellent in the properties of the obtained polyolefin is desired, and the appearance of a new transition metal compound capable of becoming such a catalyst component for olefin polymerization is desired.
Under such circumstances, metallocene improvement has been attempted, and as disclosed in, for example, Chem. Rev. 2000 (100), 1205, Chem. Rev. 2000 (100), 1223, etc., cyclopentadienyl. In the case of a bridged biscyclopentadienyl group-containing metallocene, not only the cyclopentadienyl group part but also the bridge part has been improved.

  On the other hand, as another method for improving metallocene, a method of combining a cyclopentadienyl group with other ligands has been attempted, and examples thereof include heteroatoms such as a nitrogen atom, an oxygen atom, and a phosphorus atom. Transition metal compounds containing a monocyclopentadienyl compound bonded to a cyclopentadienyl group via a bridging group such as a hydrocarbon group or a silicon-containing group as a ligand. A method for polymerizing olefins using the above is disclosed in Chem. Rev., 1998 (98), 2587, Chem. Rev., 2003 (103), 2633, and the like.

  On the other hand, as a method for improving the metallocene different from the above, there is a method of changing the crosslinking group of the bridged biscyclopentadienyl group-containing metallocene. For example, a well-known bridged biscyclopentadienyl group-containing metallocene has a structure in which two cyclopentadienyl groups are bridged via a hydrocarbon group or a silicon-containing group. Transition metal compounds containing a biscyclopentadienyl compound having a bridging moiety bridged with a boron-containing group as a ligand include Eur. J. Inorg. Chem. 1999, 1899, Organometallics, 2001 (20), 2093, etc. Is disclosed.

  Further, Organanometallics, 2000 (19), 1599, Chem. Commun., 2000, 1049, JP 2002-532508 A, Appl. Organometal. Chem., 2003 (17), 421, Dalton Trans., 2004, 938 In such a case, a monoanionic group containing a heteroatom such as a nitrogen atom, a nitrogen atom, or a phosphorus atom is bonded to a cyclopentadienyl group via a tricoordinate boron atom to form a dianion as a whole ligand. A novel transition metal compound containing a monocyclopentadienyl compound as a ligand is disclosed.

  Still further, Organometallics, 1997 (16), 4995 discloses a lithium salt of a monoindenyl compound in which a monoanion is formed as a whole ligand, in which an indenyl group and an ethoxy group are bonded via a tetracoordinate boron atom. However, a transition metal compound containing the ligand, an olefin polymerization catalyst containing the transition metal compound as a catalyst component, and a polymerization method using the olefin polymerization catalyst are not known.

  Furthermore, in Organometallics, 2000 (19), 1599, a cyclopentadienyl group and a halogen, or a hydroxyl group having an active hydrogen, an amino group, and the like are bonded via a tetracoordinate boron atom, and J. Organomet. In Chem., 2003 (680), 193, a cyclopentadienyl group and a halogen, phosphino group, or an amino group having active hydrogen are bonded via a tetracoordinate boron atom, and the whole ligand is a dianion. Monocyclopentadienyl compounds that form are reported, and in these documents, transition metal compounds containing these compounds as ligands are also disclosed. The transition metal compound of the above reported example is characterized in that it contains an additional cyclopentadienyl group simultaneously with the cyclopentadienyl group in the dianion ligand.

In view of the above situation, the polymerization performance of the catalyst containing the monocyclopentadienyl compound used in these prior arts is not yet sufficient, and a novel olefin polymerization catalyst component that has further excellent polymerization performance. The appearance of transition metal compounds has been desired.
JP 58-19309 A JP 61-130314 A JP 2002-532508 A Chem. Rev. 2000 (100), 1205 Chem. Rev. 2000 (100), 1223 Chem. Rev., 1998 (98), 2587 Chem. Rev., 2003 (103), 2633 Organometallics, 2001 (20), 2093 Eur. J. Inorg. Chem. 1999, 1899 Organometallics, 2000 (19), 1599 Chem. Commun., 2000, 1049 Appl. Organometal. Chem., 2003 (17), 421 Dalton Trans., 2004, 938 Organometallics, 1997 (16), 4995 J. Organomet. Chem., 2003 (680), 193

  In general, polyolefins are used in various fields such as for various molded products because they are excellent in mechanical properties. However, in recent years, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. Yes. However, the conventional catalyst as described above has not been sufficient in polymerization performance. Under such circumstances, there has been a demand for the appearance of an olefin polymerization catalyst capable of producing a polyolefin having excellent olefin polymerization performance and excellent properties under efficient conditions for commercial production.

  The inventors of the present invention have made extensive studies on a transition metal compound having a novel structure for synthesizing an olefin polymer that has solved the above problems and a polymerization method using the same, and are represented by the general formula (1). The present inventors have succeeded in developing a novel transition metal compound having a specific structure, and found that the above-mentioned problems can be solved by polymerization using the transition metal compound, thereby completing the present invention.

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

[In general formula (1), L is a dianionic ligand represented by the above general formula (2), wherein R ^{1 to} R ⁴ may be the same as or different from each other, a hydrogen atom, A group selected from a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, and adjacent to each other among atoms or groups represented by R ^{1 to} R ⁴ Two groups may be bonded to form an aromatic ring or an aliphatic ring together with the carbon atoms to which they are bonded, and R ⁵ and R ⁶ may be the same or different from each other, and R ¹ -R ⁴ is the same atom or group as R ^4, and two adjacent groups out of the atoms or groups represented by R ⁵ and R ⁶ are bonded together to form an aliphatic ring together with the bonded carbon atoms. A heterocycle may be formed. Q represents tetracoordinate boron, aluminum, gallium, indium, or thallium. D is a carbene or a group represented by the above general formula (3) coordinated to M through V representing a hetero atom, V represents a carbene, nitrogen, oxygen, sulfur, phosphorus atom, R ^a and R ^{b, which} may be the same or different from each other, are derived from a cyclic or acyclic hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Two groups represented by R ^a and R ^b may be combined to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. When D is a group and VR ^a R ^b , the atom where D is bonded to boron is V, and when V is oxygen, only one of R ^a and R ^b is included, and D is a group and R ^a VR ^In the case of ^b , the atom where D is bonded to boron is ^Ra , and ^Ra may be carbon or a heteroatom. M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are May be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene, or a non-conjugated branched diene Or a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, or a non-conjugated cyclic diene, and n is An integer from 0 to 3 is indicated. ]

  The present invention also provides an olefin polymerization catalyst containing the novel transition metal compound (A-2) represented by the general formula (1 ′), and an olefin polymerization method using the olefin polymerization catalyst. Objective.

[In the general formula (1 ′), L is a dianionic ligand represented by the above general formula (2 ′), wherein R ^{1 to} R ⁴ may be the same as or different from each other, hydrogen A group selected from an atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, and among the atoms or groups represented by R ^{1 to} R ⁴ , Two adjacent groups may be bonded to form an aromatic ring or an aliphatic ring together with their bonded carbon atoms, and R ⁵ and R ⁶ may be the same or different from each other; R ^{1 to} R ⁴ are the same atoms or groups, and two of the atoms or groups represented by R ⁵ and R ⁶ are adjacent to each other, and together with the carbon atoms to which they are bonded, aliphatic A ring or a heterocycle may be formed. Q represents tetracoordinate boron, aluminum, gallium, indium, or thallium. D is a group represented by the general formula (3 ′) coordinated to M through V representing carbene, heteroatom, or halogen, and V is a carbene, nitrogen, oxygen, sulfur, phosphorus atom, Represents fluorine, chlorine, bromine, iodine, and R ^a and R ^{b, which} may be the same or different from each other, are a hydrogen atom, a cyclic or acyclic hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, A group selected from a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, wherein two groups represented by R ^a and R ^b are bonded together with an aromatic ring together with their bonded carbon atoms; An aliphatic ring or a heterocyclic ring may be formed. D is a group, atom D is bonded to the boron in the case of VR ^a R ^b is a V, also V is either R ^a and R ^b in the case of nitrogen, or both may be hydrogen, V is oxygen contain only either R ^a and R ^b when also R ^a or R ^b may be hydrogen, in the case of halogen does not contain either of R ^a and R ^b, also D groups of R ^a VR ^b In this case, the atom where D is bonded to boron is ^Ra , and ^Ra may be carbon or a heteroatom. M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are May be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene, or a non-conjugated branched diene Or a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a non-conjugated cyclic diene. , N represents an integer of 0-3. ]

  The novel transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization, and polymerization of ethylene, propylene, butene, decene, etc., and copolymerization of ethylene / propylene, ethylene / butene copolymer, etc. In this case, the polymerization proceeds with high polymerization activity. When copolymerization is carried out, the copolymerization of the comonomer is extremely excellent, and an ethylene / olefin copolymer having a high comonomer content can be obtained when a small amount of comonomer is used, compared to conventional olefin polymerization catalysts. Is extremely valuable.

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

  First, the novel transition metal compound according to the present invention will be described.

  The transition metal compound (A-1) of the present invention, which is preferably used as an olefin polymerization catalyst component, is a novel transition metal compound (A-1) represented by the following general formula (1).

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

R ^{1 to} R ⁴ may be the same or different from each other, and each represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group. Specifically, halogen atoms such as fluorine, chlorine, bromine, iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl, benzyl, phenyl Hydrocarbons having 1 to 30 carbon atoms such as arylalkyl groups such as ethyl and phenylpropyl, and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl Group: the hydrocarbon having 1 to 30 carbon atoms A halogenated hydrocarbon group having 1 to 30 carbon atoms in which a halogen atom is substituted on the primary group; a silylated hydrocarbon group having 1 to 30 carbon atoms in which the silyl atom is substituted on the hydrocarbon group having 1 to 30 carbon atoms. .

Further, two groups adjacent to each other among the atoms or groups represented by R ^{1 to} R ⁴ are bonded to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. Alternatively, an indene ring or a fluorene ring may be formed.

R ⁵ and R ⁶ may be the same as or different from each other, and represent the same atom or group as R ^{1 to} R ^4, and two adjacent groups among the atoms or groups represented by R ^{5 to} R ⁶ May combine to form an aliphatic ring or a heterocycle together with the carbon atoms to which they are attached.

Q represents tetracoordinate boron, aluminum, gallium, indium, or thallium. D is a carbene or a group represented by the above general formula (3) coordinated to M through V representing a hetero atom, V represents a carbene, nitrogen, oxygen, sulfur, phosphorus atom, R ^a and R ^{b, which} may be the same or different from each other, are derived from a cyclic or acyclic hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Two groups represented by R ^a and R ^b may be combined to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. When D is a group and VR ^a R ^b , the atom where D is bonded to boron is V, and when V is oxygen, only one of R ^a and R ^b is included, and D is a group and R ^a VR ^In the case of ^b , the atom where D is bonded to boron is ^Ra , and ^Ra may be carbon or a heteroatom.

Specifically, VR ^a R ^b includes nitrogen-containing groups such as dimethylamino group, diethylamino group, diphenylamino group, pyrrolidinyl group, pyrrolyl group, piperidino group, morpholino group, methoxy group, ethoxy group, isopropoxy group, Examples thereof include oxygen-containing groups such as tertiary butoxy group and phenoxy group, phosphorus-containing groups such as dimethylphosphino group, diethylphosphino group and diphenylphosphino group. R ^a VR ^b includes imidazolyl group and pyrazolyl group. Oxygen containing cyclic nitrogen-containing groups such as triazolyl group, 2-pyridyl group, 2-quinolyl group, 2-pyridazinyl group, tetrahydrofuranyl group, 2-furyl group, 2-methoxyphenyl group, 2-morpholinyl group And sulfur-containing groups such as methylthiomethyl group, tertiary butylthiomethyl group, and 2-thienyl group It is.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group; Y represents a neutral ligand having an electron-donating group; When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different, and a plurality of groups represented by X are bonded to each other. Alternatively, a conjugated linear diene, a conjugated branched diene, a nonconjugated linear diene, or a nonconjugated branched diene may be formed, and n represents an integer of 0 to 3.

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

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

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

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

  When m is 2 or more, a plurality of atoms or groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. Aromatic rings, aliphatic rings, and non-conjugated cyclic dienes may be formed.

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

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

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

In this specification, the methyl group is Me, the ethyl group is Et, the n-propyl group is n-Pr, the i-propyl group is i-Pr, the n-butyl group is n-Bu, and the t-butyl group is t. -Bu, Adamantyl group Ad, Cumyl group Cum, Trimethylsilyl group TMS, Triphenylsilyl group TPS, Trityl group Tr, Phenyl group Nap, Tolyl group Tol, Phenanthryl group Phenanthryl, A mesityl group (2,4,6-trimethylphenyl group) may be abbreviated as Mes, a pentafluorophenyl group as C ₆ F ₅ , and a cyclopentadienyl group as Cp.

[Optional components constituting the olefin polymerization catalyst]
The present invention relates to a transition metal compound (A-2) represented by the general formula (2 ′),
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It relates to an olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds which react with transition metal compound (A-2) to form ion pairs.

Hereinafter, the transition metal compound (A-2) will be described. The transition metal compound (A-2) includes the case where D is a halogen in addition to the transition metal compound (A-1) described above. In the transition metal compound (A-2), the group represented by the general formula (3), R ^a and R ^b may be the same or different from each other, and one or both of R ^a and R ^b are hydrogen. In addition, when D is a group and VR ^a R ^b , the atom where D is bonded to boron is V, and when V is nitrogen, either R ^a or R ^b Or both can be hydrogen, and when V is oxygen, it contains only one of R ^a and R ^b , and R ^a or R ^b can be hydrogen, and when it is halogen, both R ^a and R ^b are included Absent. Furthermore, a plurality of groups represented by X in the transition metal compound (A-2) may be bonded to each other to form a ring, and in addition to the same group as in the transition metal compound (A-1), a conjugated cyclic group This includes cases where diene is formed.

Although the example of the specific structure of the transition metal compound (A-2) represented by the said General formula (1) obtained by the above is shown below, it is not limited to these.
As an example of a specific structure of the transition metal compound (A-2), in addition to the transition metal compound (A-1), a compound having a structure represented by the following can be given.

  Next, (B) component used with a transition metal compound (A-2) as an olefin polymerization catalyst is demonstrated.

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

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(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, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄
(Wherein, ^{M 2} represents a Li, Na or K, ^{R a} is from 1 to 15 carbon atoms, preferably an. 1-4 hydrocarbon group) complex of Group 1 metal and aluminum represented by Alkylates.

(B-1c) General formula R ^a R ^b M ³
(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 M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by:

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

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

General formula R ^a _m AlX _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compound

General formula R ^a _m AlH _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3),

General formula R ^a _m Al (OR ^b ) _n X _q
(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, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

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

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

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

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

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

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

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

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

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

The benzene-insoluble organoaluminum oxy compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is, relative to benzene Those that are insoluble or sparingly soluble are preferred.
Examples of the organoaluminum oxy compound include an organoaluminum oxy compound (G-1) containing boron represented by the following general formula (4).

(In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other. The organoaluminumoxy compound (G-1) containing boron represented by the general formula (4) includes an alkyl boronic acid (G-2) represented by the following general formula (5),

(Wherein R ²⁰ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

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

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

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

(B-3) Ionized ionic compound The ionized ionic compound (B-3) is a compound that reacts with the transition metal compound (A-2) to form an ion pair. Examples of such compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, US5321106, and the like. Etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

  Examples of the ionic compound include a compound represented by the following general formula (6).

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

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

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

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

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

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

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

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (7) or (8).

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

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

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

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

Other transition metal compound In the present invention, in the polymerization, the transition metal compound (A-2) and other transition metal compound, for example, a ligand containing a hetero atom such as nitrogen, oxygen, sulfur, boron or phosphorus. Known transition metal compounds can be used in combination.

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

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

  In the method for producing an olefin polymer according to the present invention, the component (A-1) or (A-2) as described above (hereinafter may be collectively referred to as component (A)) and component (B ) If necessary, olefin polymerization is performed in the presence of a catalyst composed of another transition metal compound. In the polymerization, the method of adding the component (A) to the polymerization vessel, the usage method of each component, the addition method, and the order of addition are arbitrarily selected, and the following methods are exemplified.

(1) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization reactor.
(3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.

  The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. It can also be used as a solvent.

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

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

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

Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5. When component (D is used, when component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0. In the case of component (B-2) in an amount of 1 to 5, the molar ratio of component (D) to aluminum atoms in component (B-2) [(D) / (B-2 )] Is usually 0.001 to 2, preferably 0.005 to 1 in the case of component (B-3), the molar ratio [(D) / (B-3)] is The amount is usually 0.01 to 10, preferably 0.1 to 5.

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

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

  The molecular weight and molecular weight distribution of the polyolefin obtained in the present invention can be adjusted by changing the polymerization temperature.

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

Preparation of catalyst component << [(pentafluorophenyl) ₂ B (ethoxy) (Inden-1'-yl)] TiCl ₂ synthesis >>
A toluene solution of Ti (NMe ₂ ) ₄ (0.34 g, 1.52 mmol) was cooled to −78 ° C., and Li [(pentafluorophenyl) ₂ B (ethoxy) obtained by the method described in Organometallics., 1997 (16), 4997. ) (Inden-1′-ylH)] · 2THF (1.00 g, 1.52 mmol) in toluene was gradually added dropwise, followed by reaction at room temperature for 2 hours. From the obtained solution, a solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a solid. Subsequently, hexane was added to the solid, cooled to −78 ° C., and stirred, while Me ₃ SiCl (0.19 ml, 1.52 mmol) was added. After the addition, the reaction was allowed to stir at room temperature for 5 hours. From the obtained solution, the solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a brown mixture containing the target complex.

Polymerization of ethylene 250 ml of a toluene solution was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene gas (= 100 liters / hr) at 25 ° C. Thereafter, 0.25 mmol of triisobutylaluminum and 1.0 ml of a toluene solution (5 mmol / l) of [(pentafluorophenyl) ₂ B (ethoxy) (Inden-1′-yl)] TiCl ₂ synthesized in Synthesis Example 1 were added, Subsequently, 1.2 equivalents of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to Ti to initiate polymerization. After reacting for 30 minutes at 25 ° C. in an atmosphere of normal pressure ethylene gas (= 100 liters / hr), the polymerization was terminated by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. The polymer was sufficiently washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.2 g of polyethylene.

Preparation of catalyst component << [(pentafluorophenyl) ₂ B (3,5-dimethylpyrazole) (Inden-1'-yl)] TiCl ₂ synthesis >>
Synthesis of Li [(pentafluorophenyl) ₂ B (3,5-dimethylpyrazole) (Inden-1'-ylH)]
A diethyl ether solution of (pentafluorophenyl) ₂ B (Inden-1'-ylH) (1.00 g, 2.17 mmol) obtained by the method described in Organometallics., 1997 (16), 4997 was cooled to -78 ° C, and Iorganic Chemistry , 2000 (39), 49971561, Li (3,5-metylpyrazolyl) (0.23 g, 2.17 mmol) in diethyl ether was gradually added dropwise, followed by reaction at room temperature for 3 hours. From the obtained solution, the solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a solid containing the desired compound.

Synthesis of [(pentafluorophenyl) ₂ B (3,5-dimethylpyrazole) (Inden-1'-yl)] TiCl ₂
A toluene solution of Ti (NMe ₂ ) ₄ (0.40 g, 1.78 mmol) was cooled to −78 ° C., and a toluene solution of the solid (1.00 g) obtained by the above reaction was gradually added dropwise, followed by reaction at room temperature for 2 hours. I let you. From the obtained solution, a solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a solid. Subsequently, hexane was added to the solid, cooled to −78 ° C., and stirred, while Me ₃ SiCl (0.23 ml, 1.78 mmol) was added. After the addition, the reaction was allowed to stir at room temperature for 5 hours. From the obtained solution, the solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a brown mixture containing the target complex.

Polymerization Example 1 of _{ethylene, [(pentafluorophenyl) 2 B (} ethoxy) (Inden-1'-yl)] in place of _{TiCl 2 [(pentafluorophenyl) 2 B} (3,5-dimethylpyrazole) (Inden-1'- yl)] TiCl ₂ in toluene (5 mmol / l) except that 1 ml was used for polymerization and post-treatment in the same manner as in Example 1 to obtain 0.3 g of polyethylene.

Preparation of catalyst component << [(pentafluorophenyl) ₂ B (3,5-dimethylpyrazole) (Inden-1'-yl)] ZrCl ₂ synthesis >>
A toluene solution of Zr (NMe ₂ ) ₄ (0.48 g, 1.78 mmol) was cooled to −78 ° C., and a toluene solution of the solid (1.00 g) obtained by the above reaction was gradually added dropwise, followed by reaction at room temperature for 2 hours. I let you. From the obtained solution, a solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a solid. Subsequently, hexane was added to the solid, cooled to −78 ° C., and stirred, while Me ₃ SiCl (0.23 ml, 1.78 mmol) was added. After the addition, the reaction was allowed to stir at room temperature for 5 hours. From the obtained solution, the solvent and by-products were distilled off under reduced pressure under high vacuum to obtain a brown mixture containing the target complex.

Polymerization Example 1 of _{ethylene, [(pentafluorophenyl) 2 B (} ethoxy) (Inden-1'-yl)] in place of _{TiCl 2 [(pentafluorophenyl) 2 B} (3,5-dimethylpyrazole) (Inden-1'- yl)] ZrCl ₂ in toluene (5 mmol / l) was used in the same manner as in Example 1 except that 1 ml was used, and 0.5 g of polyethylene was obtained.

Polymerization of ethylene In Example 1, instead of [(pentafluorophenyl) ₂ B (ethoxy) (Inden-1′-yl)] TiCl ₂ , the method described in J. Organomet. Chem., 2003 (680), 193 was used. Polymerization and post-treatment were carried out in the same manner as in Example 1 except that 1 ml of the resulting toluene solution (5 mmol / l) of [(pentafluorophenyl) ₂ B (t-butylamino) (Cyclopentadienyl)] TiCl (Cyclopentadienyl) was used. 0.3g was obtained.

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

Claims (7)

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

[In general formula (1), L is a dianionic ligand represented by the above general formula (2), wherein R ^{1 to} R ⁴ may be the same as or different from each other, a hydrogen atom, A group selected from a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, and adjacent to each other among atoms or groups represented by R ^{1 to} R ⁴ Two groups may be bonded to form an aromatic ring or an aliphatic ring together with the carbon atoms to which they are bonded, and R ⁵ and R ⁶ may be the same or different from each other, and R ¹ -R ⁴ is the same atom or group as R ^4, and two adjacent groups out of the atoms or groups represented by R ⁵ and R ⁶ are bonded together to form an aliphatic ring together with the bonded carbon atoms. A heterocycle may be formed. Q represents tetracoordinate boron, aluminum, gallium, indium, or thallium. D is a carbene or a group represented by the above general formula (3) coordinated to M through V representing a hetero atom, V represents a carbene, nitrogen, oxygen, sulfur, phosphorus atom, R ^a and R ^{b, which} may be the same or different from each other, are derived from a cyclic or acyclic hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Two groups represented by R ^a and R ^b may be combined to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. When D is a group and VR ^a R ^b , the atom where D is bonded to boron is V, and when V is oxygen, only one of R ^a and R ^b is included, and D is a group and R ^a VR ^In the case of ^b , the atom where D is bonded to boron is ^Ra , and ^Ra may be carbon or a heteroatom. M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are May be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene, or a non-conjugated branched diene Or a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, or a non-conjugated cyclic diene, and n is An integer from 0 to 3 is indicated. ]   The valence state of the transition metal atom M in the general formula (1) is a transition metal atom of Group 4 or Group 5 of the periodic table that is divalent, trivalent, or tetravalent. And a novel transition metal compound (A-1). The two adjacent groups among the atoms or groups represented by R ^{1 to} R ⁴ are bonded to each other to form an aromatic ring together with the carbon atoms to which the groups are bonded. The novel transition metal compound (A-1) according to either 1 or 2.   The novel transition metal compound (A-1) according to claim 3, wherein the aromatic ring is unsubstituted indene or substituted indene.   The novel transition metal compound (A-1) according to claim 3, wherein the aromatic ring is unsubstituted fluorene or substituted fluorene. A catalyst for olefin polymerization comprising transition metal compounds (A-2) and (B) having a structure represented by the following general formula (1 ′).

[In the general formula (1 ′), L is a dianionic ligand represented by the above general formula (2 ′), wherein R ^{1 to} R ⁴ may be the same as or different from each other, hydrogen A group selected from an atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, and among the atoms or groups represented by R ^{1 to} R ⁴ , Two adjacent groups may be bonded to form an aromatic ring or an aliphatic ring together with their bonded carbon atoms, and R ⁵ and R ⁶ may be the same or different from each other; R ^{1 to} R ⁴ are the same atoms or groups, and two of the atoms or groups represented by R ⁵ and R ⁶ are adjacent to each other, and together with the carbon atoms to which they are bonded, aliphatic A ring or a heterocycle may be formed. Q represents tetracoordinate boron, aluminum, gallium, indium, or thallium. D is a group represented by the general formula (3 ′) coordinated to M through V representing carbene, heteroatom, or halogen, and V is a carbene, nitrogen, oxygen, sulfur, phosphorus atom, Represents fluorine, chlorine, bromine, iodine, and R ^a and R ^{b, which} may be the same or different from each other, are a hydrogen atom, a cyclic or acyclic hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, A group selected from a silylated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, wherein two groups represented by R ^a and R ^b are bonded together with an aromatic ring together with their bonded carbon atoms; An aliphatic ring or a heterocyclic ring may be formed. D is a group, atom D is bonded to the boron in the case of VR ^a R ^b is a V, also V is either R ^a and R ^b in the case of nitrogen, or both may be hydrogen, V is oxygen contain only either R ^a and R ^b when also R ^a or R ^b may be hydrogen, in the case of halogen does not contain either of R ^a and R ^b, also D groups of R ^a VR ^b In this case, the atom where D is bonded to boron is ^Ra , and ^Ra may be carbon or a heteroatom. M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group and a nitrogen-containing group. Y represents a neutral ligand having an electron-donating group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are May be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene, or a non-conjugated branched diene Or a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a non-conjugated cyclic diene. , N represents an integer of 0-3. ]
(B) (B-1) Organometallic compound
(B-2) an organoaluminum oxy compound, and
(B-3) At least one compound selected from compounds that react with the transition metal compound (A-2) to form ion pairs.   An olefin polymerization method comprising homopolymerizing an olefin or copolymerizing two or more olefins in the presence of the olefin polymerization catalyst according to claim 6.