JP7402003B2 - Catalyst for olefin polymerization - Google Patents

Description

The present invention relates to a novel catalyst containing a complex having a specific structure, and more specifically to a catalyst composition containing a tridentate ligand complex having a nitrogen-containing heterocyclic structure as an essential component, and a catalyst composition containing the complex as an essential component. It is related to olefin polymerization by.

Olefin polymers have excellent properties such as physical properties and moldability among resin materials, and are also highly economical and environmentally friendly, making them extremely versatile and important industrial materials.
However, since olefin polymers do not have polar groups, it is difficult to apply them to applications that require physical properties such as adhesion with other materials, printability, or compatibility with fillers. There are many. In particular, polyethylene resin has a low density and poor mechanical properties due to short chain branches such as ethyl branching, and it cannot be used alone or as a composition with other resins. , its scope of application is limited.

In order to solve these problems, in recent years, late transition metal complex catalysts called post-metallocenes have been developed, and physical properties of olefin polymers have been controlled using the catalysts. As post-metallocene catalysts for olefin polymerization, iron catalysts such as tridentate iron complexes having a diiminopyridine skeleton and bisaryliminopyridine iron are used, and the results of ethylene polymerization using these catalysts are known ( Patent documents 1 to 3, non-patent document 1).
Many tridentate ligands are known and are used in a wide variety of catalytic reactions. For example, compounds having a carbazole skeleton and compounds having an isoindoline skeleton are also known (Non-Patent Documents 2, 3, 4).

Special Publication No. 2006-501067 Patent No. 4108141 Special Publication No. 2002-513823

Organometallics, 2005, 24, 4878-4881 Tetrahedron 66 (2010) 7707-7719 J. Am. Chem. Soc. 2012, 134, 13538-13541 J. Am. Chem. Soc. 2016, 138, 4972-4983

Ethylene polymerization using an iron complex has been reported as described above, but in Patent Document 1, addition of a zinc compound is essential to reduce short chain branching, and in the case of polymerization without addition. , the number of ethyl branches is high. Furthermore, in Non-Patent Document 1, when MMAO is used in the polyethylene obtained, the number of ethyl branches is 9 to 17/1000C, and a satisfactory product is not obtained. Patent Document 3 also evaluates PP polymerization, but the details of the obtained polymer are unknown. Even for transition metal complexes having ligands other than metallocenes, as in Non-Patent Documents 2 and 3, there are no known examples in which polymerization has been evaluated in detail. Thus, it is desired to develop a catalyst that can control the occurrence of branching in olefin polymerization and make it possible to produce polyolefins with excellent properties, especially polyethylene with few ethyl branches.

An object of the present invention is to create a catalyst system that effectively functions as an olefin polymerization catalyst, making it possible to produce an olefin polymer with excellent properties, especially an ethylene polymer with a small amount of branching. As a result of intensive studies aimed at solving the above problems, the present inventors discovered that a catalyst containing a specific transition metal complex functions as a component of a polymerization catalyst that meets the above purpose, and has developed the present invention. I came to create it.

［式（１）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^ｄは、各々独立して、水素原子、ハロゲン原子、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^e（Ｒ^eは、水素原子又は炭素数１～３０の炭化水素基を示す）で置き換えられていてもよい炭素数１～３０の炭化水素基、ハロゲン原子で置換された炭素数１～３０の炭化水素基、及び炭素数１～３０の炭化水素基で置換されたシリル基からなる群より選択される置換基を示し、
Ｃ^１及びＣ^２は、炭素原子であり、
Ｚ^１及びＺ^２は、各々独立して、直接結合であるか、又は不飽和結合若しくはヘテロ原子を含んでいてもよい炭素数１～３０の２価の炭化水素基であり、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、Ｚ^１とＣ^１、Ｚ^２とＣ^２、Ｃ^１とＡ、又はＡとＣ^２の結合は、少なくとも１つが不飽和結合を形成していてもよく、
Ａは、不飽和結合を含んでいてもよい炭素数１～４の２価の直鎖状炭化水素基であり、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、
Ｚ^１中の２点、Ｚ^２中の２点、Ａ中の２点、Ｚ^１とＡ又はＺ^２とＡの組は、１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^e（Ｒ^eは、水素原子又は炭素数１～３０の炭化水素基を示す）で置き換えられていてもよい、直鎖若しくは分岐鎖状の炭素数１～３０の２価の炭化水素基によって連結され、飽和若しくは不飽和の環を形成していてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
Ｒ^２０、Ｒ^２１は、各々独立して、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい炭素数１～３０の炭化水素基、ハロゲン原子で置換された炭素数１～３０の炭化水素基、及び炭素数１～３０の炭化水素基で置換されたシリル基からなる群より選択される置換基を示し、
Ｍは、周期表８～１０族の遷移金属からなる群より選択される金属原子を示し、
Ｑは酸素原子、硫黄原子又は窒素原子を表し、Ｑを含む環状構造内には、不飽和結合を含んでいてもよく、
Ｙは、窒素原子又はリン原子であり、
ｎは、１又は２であり、
ｍは、１から３の整数であり、
ｐは、０又は１であり、
Ｘは、炭素数１～２０の炭化水素基、酸素原子若しくは窒素原子を含む炭素数１～２０の炭化水素基、炭素数１～１０のアルコキシ基、炭素数６～２０のアリーロキシ基、炭素数２～１０のアシル基、炭素数２～１０のアシルオキシ基、カルボキシル基、炭素数２～１０のエステル基、アミノ基、炭素数１～１２の置換アミノ基、及びハロゲンからなる群より選択される置換基を示す。］ The catalyst constituting the basic invention (first invention) of the present invention is an α-olefin polymerization catalyst characterized by containing a transition metal complex represented by the following general formula (1).

[In formula (1),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^d are each independently a hydrogen atom, a halogen atom, or one or more methylene groups (-CH ₂ -) other than the terminal are O, S, or NR ^e (R ^e represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), a hydrocarbon group having 1 to 30 carbon atoms that may be substituted with a halogen atom, and 1 to 30 carbon atoms substituted with a halogen atom; represents a substituent selected from the group consisting of a hydrocarbon group and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms,
C ¹ and C ² are carbon atoms,
Z ¹ and Z ² are each independently a direct bond or a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an unsaturated bond or a hetero atom; may be substituted with one or more substituents represented by R ^1' (where R ^1' is the same as R ¹ ), Z ¹ and C ¹ , Z ² and C ² , C ¹ At least one of the bonds between and A, or A and ^C2 may form an unsaturated bond,
A is a divalent linear hydrocarbon group having 1 to 4 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (here, R ^1' is R ¹ and may be substituted with one or more substituents shown in (synonymous),
The two points in Z ¹ , the two points in Z ² , the two points in A, and the set of Z ¹ and A or Z ² and A are such that one or more methylene groups (-CH ₂ -) are O, S or By a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with NR ^e (R ^e represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms) may be connected to form a saturated or unsaturated ring, and the ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group,
R ²⁰ and R ²¹ are each independently a hydrocarbon group having 1 to 30 carbon atoms in which one or more methylene groups (-CH ₂ -) other than the terminal may be replaced with O, S or NR ^e ; , a substituent selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms,
M represents a metal atom selected from the group consisting of transition metals of Groups 8 to 10 of the periodic table,
Q represents an oxygen atom, a sulfur atom or a nitrogen atom, and the cyclic structure containing Q may contain an unsaturated bond,
Y is a nitrogen atom or a phosphorus atom,
n is 1 or 2,
m is an integer from 1 to 3,
p is 0 or 1,
X is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a carbon number selected from the group consisting of an acyl group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, a carboxyl group, an ester group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, and a halogen. Indicates a substituent. ]

By using the catalyst or catalyst composition of the present invention, it is possible to efficiently produce an olefin polymer with excellent properties, particularly an ethylene polymer with a small amount of branching. The catalyst or catalyst composition for polyolefin polymerization using a metal complex of the present invention and the method for polymerizing olefin using the same are very useful from an industrial viewpoint.

Below, the catalyst or catalyst composition of the present invention and the method for producing an olefin polymer using the same will be explained in detail for each item.

<Transition metal complex>
(1) Basic configuration The catalyst or catalyst composition in the present invention contains a transition metal complex having a tridentate ligand and represented by the above general formula (1). Here, the tridentate ligand is a heterocycle-containing compound having three heterocyclic structures, each of which can have a heteroatom as a coordination site for a transition metal. That is, in the heterocycle-containing compound, a monocyclic or fused ring (first ring) consisting of a 4- to 7-membered heterocycle containing a nitrogen atom or a phosphorus atom is directly or via a linker, It is bonded at two points to a ring structure (second and third rings) having a set of heteroatoms selected from the group consisting of two nitrogen atoms, a nitrogen atom and an oxygen atom, a nitrogen atom and a sulfur atom. The type of the first ring is not particularly limited as long as it is a 4- to 7-membered heterocycle containing a nitrogen atom or a phosphorus atom. Preferably, the heterocyclic moiety is a 5-membered ring. Further, a condensed ring such as carbazole can also be used. At this time, each ring constituting the condensed ring may also serve as a bonding point with the second and third rings as a linker. Non-limiting examples of structures formed by the first ring include pyrrole, piperidine, morpholine, phosphole, pyridine, pyrazine, pyrimidine, carbazole, isoindoline, acridine, and the like. There are no particular limitations on the type of structure that the second and third rings have, as long as the set of heteroatoms is a 5- to 7-membered ring in which one carbon atom exists. A five-membered ring is preferred. One of the nitrogen atoms may form a double bond with an adjacent carbon atom. Non-limiting groups with such a ring structure include a dihydroxazolyl group, an oxazolyl group, a dihydro-1,3-oxazinyl group, and a tetrahydro-1,3-oxazepinyl group (a combination of a nitrogen atom and an oxygen atom); Dihydroimidazolyl group, tetrahydropyrimidinyl group, hexahydropyrimidinyl group (two nitrogen atoms); dihydrothiazolyl group, dihydro-1,3-thiazinyl group, tetrahydro-1,3-thiazepinyl group (two nitrogen atoms and two nitrogen atoms); combination), etc.

"Hydrocarbon group" means a structure consisting of a carbon skeleton having a specified number of carbon atoms, and includes a linear or branched alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, Includes structures formed by bonding two or more of these groups, such as cycloalkynyl groups, aryl groups, benzyl and biphenyl groups. In addition, in this specification, a "hydrocarbon group" usually refers to a monovalent group, but if it is specified that it has a valence of two or more, the "hydrocarbon group" refers to the above group or Indicates a structure in which at least one hydrogen atom in the structure is replaced with a bond depending on the valence.

The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Examples of alkyl groups and cycloalkyl groups are methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, t-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group. group, 1-octyl group, 1-nonyl group, 1-decyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, These include decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, and 5-decyl group. Among these, preferred substituents are methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, and cyclohexyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cinnamyl group, and a styryl group.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group, and a substituent may be present on the aromatic ring of these aryl groups. Examples of substituents that may be present include alkyl groups, aryl groups, fused aryl groups, phenylcyclohexyl groups, phenylbutenyl groups, tolyl groups, xylyl groups, p-ethylphenyl groups, and the like. Among these, preferred aryl groups are phenyl group and substituted phenyl group, and preferred specific examples of substituents for substituted phenyl group are methyl group, ethyl group, t-butyl, and phenyl group, and further, Particularly preferred is a methyl group. Further, a diphenylmethyl group can also be mentioned.

"Halogen atom" means an element belonging to Group 17 of the periodic table, and specifically includes fluorine, chlorine, bromine, and iodine, and preferably chlorine. The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom preferably has a structure in which the hydrogen atom of the above-mentioned hydrocarbon group having 1 to 30 carbon atoms is substituted with one or more halogen atoms. Specific preferred examples include trifluoromethyl group and pentafluorophenyl group.

"Alkoxy group" means a hydrocarbon group having an oxygen atom bonded to its terminal, but not having the oxygen bonded to an aromatic ring. Preferably, it is an alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1-butoxy group, and t-butoxy group. Among these, more preferred substituents are methoxy, ethoxy, and isopropoxy, with methoxy being particularly preferred.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group preferably has a structure in which the above-mentioned hydrocarbon group having 1 to 30 carbon atoms is substituted with an alkoxy group. Specific preferred examples include methoxymethyl group and methoxyethyl group.

"Silyl group" means a substituent having a silicon atom at the end, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms is preferably substituted with a hydrocarbon group having 3 to 18 carbon atoms. It is a silyl group, and preferred specific examples are trimethylsilyl group, dimethylphenylsilyl group, diphenylmethylphenylsilyl group, and triphenylsilyl group. Among these, a more preferred substituent is a trimethylsilyl group or a dimethylphenylsilyl group, and particularly preferred is a trimethylsilyl group.

X is a monovalent group bonded to the central metal M, and is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or an alkoxy group having 1 to 10 carbon atoms. group, aryloxy group having 6 to 20 carbon atoms, acyl group having 2 to 10 carbon atoms, acyloxy group having 2 to 10 carbon atoms, carboxyl group, ester group having 2 to 10 carbon atoms, amino group, having 1 to 12 carbon atoms Indicates a substituent selected from the group consisting of a substituted amino group and a halogen.

"Containing an oxygen atom or a nitrogen atom" means that one or more methylene groups (-CH ₂ -) other than the terminals of a hydrocarbon group are replaced with an oxygen atom or a nitrogen atom. However, two or more adjacent carbon atoms are not replaced. When substituted with a nitrogen atom, it can constitute a secondary amino group or a tertiary amino group.

The alkoxy group having 1 to 10 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1-butoxy group, and Such as t-butoxy group. Among these, more preferred substituents are methoxy, ethoxy, and isopropoxy, with methoxy being particularly preferred.

The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, and 2,6-dimethylphenoxy group. 3,5-di-t-butylphenoxy group and 2,6-di-t-butylphenoxy group. Among these, more preferable substituents include phenoxy group, 3,5-di-t-butylphenoxy group, and 2,6-dimethylphenoxy group, and particularly preferable substituents include phenoxy group, 3,5-di-t-butylphenoxy group, and 2,6-dimethylphenoxy group. It is a t-butylphenoxy group.

The acyl group having 2 to 10 carbon atoms is preferably an acyl group having 2 to 8 carbon atoms, and specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, Examples include benzoyl group. Among these, more preferred substituents are acetyl group, pivaloyl group, and benzoyl group, and particularly preferred is benzoyl group.

The acyloxy group having 2 to 10 carbon atoms is a group represented by RC(=O)O- (where R represents a hydrocarbon group having 1 to 9 carbon atoms), and is preferably a group having 2 to 9 carbon atoms. 8 is an acyloxy group. In this case, preferred examples of R include hydrocarbon groups having 1 to 7 carbon atoms.

The ester group having 2 to 10 carbon atoms is preferably an ester group having 2 to 8 carbon atoms, and specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n- Examples include butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy)carbonyl group, (4-glycidylbutoxy)carbonyl group, phenoxycarbonyl group, succinic anhydride group, and succinimide group.
Among these, more preferred substituents include a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy)carbonyl group, and a succinic anhydride group, and particularly preferred are a methoxycarbonyl group and a succinic anhydride group. It is the basis.

Preferred specific examples of the substituted amino group having 1 to 12 carbon atoms include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, monophenylamino group, diphenylamino group, bis Examples include (trimethylsilyl)amino group and morpholinyl group. Among these, more preferred substituents are dimethylamino group and diphenylamino group.

Y in general formula (1) is a nitrogen atom or a phosphorus atom. That is, the transition metal complex represented by the general formula (1) has three heteroatoms selected from the group of three nitrogen atoms or two nitrogen atoms and one phosphorus atom, and the metal atom represented by M has a tridentate structure. It has a coordinating ligand. Although the phosphorus atom tends to have good coordination ability to the metal atom species represented by M, from the viewpoint of ease of synthesizing the entire ligand, it is more preferable that Y be a nitrogen atom.

A in the general formula (1) is a divalent linear hydrocarbon group having 1 to 4 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (where R ^{1 '} may be substituted with one or more substituents represented by (synonymous with R ¹ above). Therefore, the transition metal complex represented by the general formula (1) has a 4- to 7-membered heterocycle consisting of the Y, A, and carbon atoms C ¹ and C ² .

In general formula (1), Z ¹ and Z ² are each independently a direct bond or a divalent group having 1 to 30 carbon atoms which may contain an unsaturated bond or a hetero atom. is a hydrocarbon group, and the hydrocarbon group may be substituted with one or more substituents represented by R ^1' (herein, R ^1' has the same meaning as R ¹ ). Furthermore, in the combination of two points in Z ¹ , two points in Z ² , Z ¹ and A, or Z ² and A, one or more methylene groups (-CH ₂ -) are O, S or NR ^e (R ^e represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), connected by a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms, and saturated Alternatively, an unsaturated ring may be formed, and the ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group.
Z ¹ and Z ² connect the heterocycle containing Y with two heterocycles having a nitrogen atom and Q, or form a fused ring structure together with the heterocycle containing Y, The ligand portion of the transition metal complex represented by the general formula (1) is present as a tridentate ligand. From the viewpoint of ligand design, Z ¹ and Z ² are, for example, methylene groups or are linked to the above A to form a condensed ring, so that two carbon atoms are interposed between Y and the heterocycle. It is preferable to design it as follows. One or more substituents having the same range as the definition of R ¹ may be substituted on the hydrocarbon group.

In general formula (1), the structure consisting of Y, C ¹ , C ² , A, Z ¹ and Z ² is, for example, Z ¹ and C ¹ , Z ² and C ² , C ¹ and A, or A and C ² At least one of the bonds may form an unsaturated bond.

In general formula (1), the substituents including R ¹ , R ² , R ¹¹ , and R ¹² produce an asymmetric carbon atom in the first to third rings, or themselves are asymmetric carbon atoms. It may be a group having the following. In this case, the complex represented by general formula (1) can have any steric configuration, but is preferably a single optical isomer species. In particular, combinations in which R ¹ and R ¹¹ are hydrogen atoms and R ² and R ¹² are substituents other than hydrogen, or combinations in which R ² and R ¹² are hydrogen atoms and R ¹ and R ¹¹ are substituents other than hydrogen are particularly preferred. preferable.

M represents a metal atom selected from the group consisting of transition metals of Groups 8 to 10, and specific examples thereof include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, rhenium, and platinum. Preferably iron, cobalt, nickel or palladium.

n is a value determined by the valence of the metal atom represented by M, and is an integer of 1 or 2. Further, in addition to X, M may be coordinated with a neutral ligand. Specific examples include carbonyl, triphenylphosphine, acetonitrile, pyridine, and tetrahydrofuran.

Q represents an oxygen atom, nitrogen atom, or sulfur atom, and specifies the type of heteroatom other than nitrogen that the heterocycle has. m is an integer specifying the number of ring members of the heterocycle, and is in the range of 1 to 3. Therefore, the transition metal complex represented by the general formula (1) has two 5- to 7-membered heterocyclic structures. Further, the heterocycle may have an unsaturated bond. Preferably, the unsaturated bond exists between the carbon atom to which Z ¹ or Z ² is bonded and the nitrogen atom that the heterocycle necessarily has.

R ²⁰ and R ²¹ are groups present when Q is a nitrogen atom. Therefore, when Q is a nitrogen atom, the value of p in general formula (1) is 1, and when Q is an oxygen atom or a sulfur atom, the value of p is 0.

［式（１Ａ）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｚ^１、Ｚ^２、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｚ^３及びＺ^４は，各々独立して，不飽和結合を含んでいてもよく、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい炭素数１～３０の炭化水素基又は水素原子を示し、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、或いはＺ^３はＣ^１又はＡ’と一緒になって二重結合を形成していてもよく、Ｚ^４はＣ^２又はＡ’と一緒になって二重結合を形成していてもよく、
Ｚ^１とＺ^３、Ｚ^２とＺ^４、Ｚ^３とＺ^４、Ｚ^３とＡ’、Ｚ^４とＡ’は、互いに連結して、不飽和結合を含んでいてもよい炭素環式若しくは複素環式の環構造を形成していてもよく，該環構造は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
Ｚ^１とＣ^１、Ｚ^２とＣ^２は、不飽和結合を形成していてもよく、
Ａ’は、不飽和結合を含んでいてもよい炭素数１又は２の２価の直鎖状炭化水素基であり、該炭化水素基はＺ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよい。］ As a further embodiment of the transition metal complex represented by the general formula (1), the α-olefin polymerization catalyst of the present invention more preferably contains a transition metal complex represented by the following general formula (1A).

[In formula (1A),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , Z ¹ , Z ² , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above. can be,
Z ³ and Z ⁴ may each independently contain an unsaturated bond, and one or more methylene groups (-CH ₂ -) other than the terminals may be replaced with O, S or NR ^e . It represents a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, and the hydrocarbon group is substituted with one or more substituents represented by R ^1' (herein, R ^1' has the same meaning as R ¹ ). or Z ³ may form a double bond together with C ¹ or A', and Z ⁴ may form a double bond together with C ² or A'. You can also
Z ¹ and Z ³ , Z ² and Z ⁴ , Z ³ and Z ⁴ , Z ³ and A', and Z ⁴ and A' are connected to each other to form a carbocyclic or heterocyclic group which may contain an unsaturated bond. It may form a cyclic ring structure, and the ring structure may be substituted with one or more substituents represented by R ^{1 '} (where R 1' is synonymous with R ¹ ). Often, the ring may be further fused with an alicyclic, heterocyclic, or aromatic group,
Z ¹ and C ¹ and Z ² and C ² may form an unsaturated bond,
A' is a divalent linear hydrocarbon group having 1 or 2 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is Z ^1' (here, R ^1' is R ¹ and may be substituted with one or more substituents shown in (synonymous). ]

［式（１Ｂ）中，
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｒ^３～Ｒ^７及びＲ^１３～Ｒ^１７は、各々独立して、Ｒ^１と同義であるか、或いは、Ｒ^３とＲ^７、Ｒ^７とＡ’、Ａ’とＲ^１７、Ｒ^１７とＲ^１３の組は、各々一緒になって、１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい、直鎖若しくは分岐鎖状の炭素数１～３０の２価の炭化水素基によって連結され、飽和若しくは不飽和の環を形成していてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
Ａ’は、不飽和結合を含んでいてもよい炭素数１又は２の２価の直鎖状炭化水素基であり、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよい。］ In a more preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1B).

[In formula (1B),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above,
R ³ to R ⁷ and R ¹³ to R ¹⁷ each independently have the same meaning as R ¹ , or R ³ and R ⁷ , R ⁷ and A', A' and R ¹⁷ , R ¹⁷ and R Each of the ¹³ groups together represents a linear or branched chain having 1 to 30 carbon atoms, in which one or more methylene groups (-CH ₂ -) may be replaced with O, S, or NR ^e . may be connected by a divalent hydrocarbon group to form a saturated or unsaturated ring, and the ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group,
A' is a divalent linear hydrocarbon group having 1 or 2 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (herein, R ^1' is R ¹ may be substituted with one or more substituents shown in (synonymous with). ]

［式（１Ｃ）中，
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｒ^３、Ｒ^７、Ｒ^１３及びＲ^１７は、各々独立して、Ｒ^１と同義であるか、或いは、
Ｒ^３及びＲ^７並びに／又はＲ^１３及びＲ^１７は、各々一緒になって、１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい、直鎖若しくは分岐鎖状の炭素数１～３０の２価の炭化水素基によって連結され、飽和若しくは不飽和の環を形成していてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
Ａ’は、不飽和結合を含んでいてもよい炭素数１又は２の２価の直鎖状炭化水素基であり、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、下記：

で示される構造に含まれている結合は、Ｙを含む結合を除く少なくとも１つが、二重結合を形成している。］ In a further preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1C).

[In formula (1C),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above,
R ³ , R ⁷ , R ¹³ and R ¹⁷ are each independently synonymous with R ¹ or
R ³ and R ⁷ and/or R ¹³ and R ¹⁷ each together represent a straight chain in which one or more methylene groups (-CH ₂ -) may be replaced with O, S or NR ^e Alternatively, they may be connected by a branched divalent hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring, and the ring may be an alicyclic group, a heterocyclic group, or an aromatic group. The group may be further fused,
A' is a divalent linear hydrocarbon group having 1 or 2 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (herein, R ^1' is R ¹ may be substituted with one or more substituents shown in (synonymous with), and the following:

At least one of the bonds included in the structure shown by , excluding the bond containing Y, forms a double bond. ]

［式（１Ｄ）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｍ、ｎ、Ｘは、前記定義のとおりであり、
Ｒ^３１～Ｒ^３３、Ｒ^４１～Ｒ^４３は、各々独立して、水素原子、ハロゲン原子、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^e（Ｒ^eは、水素原子又は炭素数１～３０の炭化水素基を示す）で置き換えられていてもよい炭素数１～３０の炭化水素基、ハロゲン原子で置換された炭素数１～３０の炭化水素基、及び炭素数１～３０の炭化水素基で置換されたシリル基からなる群より選択される置換基を示し、
Ａ’は、不飽和結合を含んでいてもよい炭素数１～２の直鎖状炭化水素基であり、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよい。］ In a further preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1D).

[In formula (1D),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , M, n, and X are as defined above,
R ³¹ to R ³³ and R ⁴¹ to R ⁴³ each independently represent a hydrogen atom, a halogen atom, or one or more methylene groups (-CH ₂ -) other than the terminal are O, S, or NR ^e (R ^e is , a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms), a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a halogen atom, and Indicates a substituent selected from the group consisting of a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms,
A' is a linear hydrocarbon group having 1 to 2 carbon atoms that may contain an unsaturated bond, and the hydrocarbon group is R ^1' (here, R ^1' is synonymous with R ¹ may be substituted with one or more substituents shown in ). ]

［式（１ａ）中，
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｚ^１、Ｚ^２、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｚ^３及びＺ^４は、各々独立して、不飽和結合を含んでいてもよく、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい炭素数１～３０の炭化水素基又は水素原子を示し、該炭化水素基は、Ｒ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、或いは、
Ｚ^１とＺ^３、Ｚ^２とＺ^４、Ｚ^３とＺ^４は、互いに連結して、不飽和結合を含んでいてもよい炭素環式若しくは複素環式の環構造を形成していてもよく、当該環はＲ^１’（ここでＲ^１’は、Ｒ^１と同義である）で示される置換基で１つ以上置換されていてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
Ｚ^１、Ｚ^２、Ｚ^３、Ｚ^４を有し、Ｙを含む５員環は、不飽和結合を含んでいてもよい。］
本態様は、前記式（１）におけるＡが炭素数２の直鎖状炭化水素基である場合、すなわちＹを含むヘテロ環が５員環を形成する場合に相当する。 In another preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1a).

[In formula (1a),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , Z ¹ , Z ² , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above. can be,
Z ³ and Z ⁴ may each independently contain an unsaturated bond, and one or more methylene groups (-CH ₂ -) other than the terminals may be replaced with O, S or NR ^e . It represents a hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, and the hydrocarbon group is substituted with one or more substituents represented by R ^1' (herein, R ^1' has the same meaning as R ¹ ). may have been done, or
Z ¹ and Z ³ , Z ² and Z ⁴ , and Z ³ and Z ⁴ may be connected to each other to form a carbocyclic or heterocyclic ring structure that may contain an unsaturated bond. , the ring may be substituted with one or more substituents represented by R ^1' (where R ^1' is the same as R ¹ ), and the ring may be an alicyclic group, a heterocyclic group, Alternatively, the aromatic group may be further condensed,
The five-membered ring having Z ¹ , Z ² , Z ³ , and Z ⁴ and containing Y may contain an unsaturated bond. ]
This embodiment corresponds to the case where A in the formula (1) is a linear hydrocarbon group having 2 carbon atoms, that is, the heterocycle containing Y forms a 5-membered ring.

［式（１ｂ）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｒ^３～Ｒ^７及びＲ^１３～Ｒ^１７は、各々独立して、Ｒ^１と同義であるか、或いは、Ｒ^３とＲ^７、Ｒ^７とＲ^１７、Ｒ^１７とＲ^１３の組は、各々一緒になって、１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい、直鎖若しくは分岐鎖状の炭素数１～３０の２価の炭化水素基によって連結され、飽和若しくは不飽和の環を形成していてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよい。］ In another preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1b).

[In formula (1b),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above,
R ³ to R ⁷ and R ¹³ to R ¹⁷ are each independently synonymous with R ¹ , or the pairs of R ³ and R ⁷ , R ⁷ and R ¹⁷ , and R ¹⁷ and R ¹³ are each Straight chain or branched divalent hydrocarbons having 1 to 30 carbon atoms, in which one or more methylene groups (-CH ₂ -) may be replaced with O, S or NR ^e They may be connected by a group to form a saturated or unsaturated ring, and the ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group. ]

［式（１ｃ）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｒ^２０、Ｒ^２１、Ｍ、Ｑ、Ｙ、ｎ、ｍ、ｐ、Ｘは、前記定義のとおりであり、
Ｒ^３、Ｒ^７、Ｒ^１３及びＲ^１７は、各々独立して、Ｒ^１と同義であるか、或いは、
Ｒ^３及びＲ^７並びに／又はＲ^１３及びＲ^１７は、各々一緒になって、１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^eで置き換えられていてもよい、直鎖若しくは分岐鎖状の炭素数１～３０の炭化水素基によって連結され、飽和若しくは不飽和の環を形成していてもよく、当該環は脂環族、ヘテロ環式基、若しくは芳香族基が更に縮合していてもよく、
下記：

で示される構造に含まれている結合は、Ｙを含む結合を除く少なくとも１つが、二重結合を形成している。］ In another preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1c).

[In formula (1c),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined above,
R ³ , R ⁷ , R ¹³ and R ¹⁷ are each independently synonymous with R ¹ or
R ³ and R ⁷ and/or R ¹³ and R ¹⁷ each together represent a straight chain in which one or more methylene groups (-CH ₂ -) may be replaced with O, S or NR ^e Alternatively, they may be connected by a branched hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring, and the ring may further include an alicyclic group, a heterocyclic group, or an aromatic group. May be condensed,
the below described:

At least one of the bonds included in the structure shown by , excluding the bond containing Y, forms a double bond. ]

［式（１ｄ）中、
Ｒ^１、Ｒ^２、Ｒ^１１、Ｒ^１２、Ｒ^ａ～Ｒ^e、Ｍ、ｎ、Ｘは、前記定義のとおりであり、
Ｒ^３１～Ｒ^３３、Ｒ^４１～Ｒ^４３は、各々独立して、水素原子、ハロゲン原子、末端以外の１つ以上のメチレン基（－ＣＨ_２－）がＯ、Ｓ又はＮＲ^e（Ｒ^eは、水素原子又は炭素数１～３０の炭化水素基を示す）で置き換えられていてもよい炭素数１～３０の炭化水素基、ハロゲン原子で置換された炭素数１～３０の炭化水素基、アルコキシ基で置換された炭素数２～３０の炭化水素基、及び炭素数１～３０の炭化水素基で置換されたシリル基からなる群より選択される置換基を示す。］ In another preferred embodiment, the α-olefin polymerization catalyst of the present invention is characterized by containing a transition metal complex represented by the following general formula (1d).

[In formula (1d),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , M, n, and X are as defined above,
R ³¹ to R ³³ and R ⁴¹ to R ⁴³ each independently represent a hydrogen atom, a halogen atom, or one or more methylene groups (-CH ₂ -) other than the terminal are O, S, or NR ^e (R ^e is , hydrogen atom or hydrocarbon group having 1 to 30 carbon atoms), a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, alkoxy A substituent selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms substituted with a group, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms. ]

Preferred specific examples of transition metal complexes having tridentate ligands represented by formulas (1), (1A) to (1D), and (1a) to (1d) include the following compounds. These are examples, and it is obvious that the invention is not limited to these.

<Synthesis of metal complexes>
(1) Basic synthetic route The transition metal complex represented by general formula (1) can be synthesized using methods known to those skilled in the art. That is, it can be obtained by reacting a heterocycle-containing compound as a ligand with a complex precursor containing a transition metal. As a method for synthesizing the ligand, methods known to those skilled in the art can also be used. Specific synthesis examples are described in detail as examples of ligand synthesis in Examples. The synthetic route for a metal complex obtained by reacting a complex precursor and a ligand can be arbitrarily determined based on the structure of the target compound.

(2) Complex precursor The complex precursor is a transition metal compound of Groups 8 to 10. Preferred specific examples are divalent or trivalent iron, zero-valent or divalent nickel, or palladium compounds or complexes, particularly metal halides such as iron chloride, nickel chloride, palladium chloride; iron acetate, palladium acetate, etc. acetate; a complex having a ligand such as carbonyl, triphenylphosphine, acetylacetone, η ⁴ -cyclooctadiene, acetonitrile, or pyridine.

(3) Reaction with complex precursor The amount of the complex precursor used in the present invention is usually 0.5 to 3 mol, preferably 0.7 to 3 mol, per 1 mol of the heterocycle-containing compound as a ligand. The range is 1.5 moles. The complex synthesis reaction may be carried out in the reactor used for copolymerization with the α-olefin, or may be carried out in a separate container from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without being isolated.

<Second component>
In a further embodiment, the catalyst composition of the present invention comprises a transition metal complex represented by any of the general formulas (1), (1A) to (1D), and (1a) to (1d) as component (A). In addition, as component (B), it contains a compound or ion-exchangeable layered silicate that reacts with component (A) to form an ion pair.

(1) Compounds that react with component (A) to form ion pairs Organoaluminumoxy compounds, which are one of component (B), can be mentioned as compounds that react with component (A) to form ion pairs. . The organoaluminumoxy compound has an Al--O--Al bond in its molecule, and the number of such bonds is usually in the range of 1 to 100, preferably 1 to 50. Such an organoaluminumoxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As inert hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene can be used, but aliphatic hydrocarbons or Preference is given to using aromatic hydrocarbons.

As the organoaluminum compound used for preparing the organoaluminumoxy compound, any compound represented by the following general formula can be used, but trialkylaluminum is preferably used.
(R ₁ ) _t Al(X ₃ ) _(3-t)
(In the above formula, R ₁ represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and X ₃ represents a hydrogen atom or a halogen atom. (t is an integer of 1≦t≦3.)
The alkyl group of trialkylaluminum can be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc., but methyl group , isobutyl group is preferred, and methyl group is particularly preferred. Two or more of the above organoaluminum compounds can also be used in combination.

The reaction ratio between water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly 0.5/1 to 1/1, and the reaction temperature is , usually in the range of -70 to 100°C, preferably in the range of -20 to 20°C. The reaction time is usually selected within the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components that can generate water in the reaction system can also be used. Among the organoaluminoxane compounds mentioned above, those obtained by reacting aluminum alkyl with water are usually called aluminoxanes, and in particular, methylaluminoxane (including those consisting essentially of methylaluminoxane (MAO)). is suitable as an organoaluminumoxy compound. Solid dry methylaluminoxane (DMAO) obtained by evaporating the MAO solution is also suitable.
Of course, it is also possible to use a combination of two or more of the above-mentioned organoaluminumoxy compounds as the organoaluminumoxy compound, or a solution in which the above-mentioned organoaluminumoxy compound is dissolved or dispersed in the above-mentioned inert hydrocarbon solvent. You may also use the following.

Other specific examples of component (B) include borane compounds and borate compounds. More specifically, the above borane compounds include triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tris(o-fluorophenyl)borane, tris( p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris (3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane, tris Examples include (perfluoroanthryl)borane and tris(perfluorobinaphthyl)borane.

Among these, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluoronaphthyl)borane, Biphenyl)borane, tris(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane are more preferred, and even more preferred are tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, and tris( Preferred examples include perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane.

Further, specifically representing the borate compound, the first example is a compound represented by the following general formula.
[L1-H] ⁺ [B(R2)(R3)(X4)(X5)] ^-
In the above formula, L1 is a neutral Lewis base, and [L1-H] represents a Bronsted acid such as ammonium, anilinium, or phosphonium.
Examples of ammonium include trialkyl-substituted ammoniums such as trimethylammonium, triethylammonium, tripropylammonium, tri(t-butyl)ammonium, and tri(n-butyl)ammonium, and dialkylammoniums such as di(n-propyl)ammonium and dicyclohexylammonium. can be exemplified. Examples of anilinium include N,N-dialkylanilinium such as N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-dimethyl-2,4,6-pentamethylanilinium. .
Furthermore, examples of the phosphonium include triarylphosphoniums and trialkylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

Furthermore, in the above general formula, R2 and R3 are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. Preferred substituents for the substituted aromatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and isopropyl, and halogen atoms such as fluorine, chlorine, bromine, and iodine. Furthermore, X4 and X5 are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted hydrocarbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced with a halogen atom; It is.

Specific examples of the compound represented by the above general formula include tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethyl phenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6-ditrifluoromethyl) phenyl)borate, dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(2,6-difluorophenyl)borate, dimethylaniliniumtetra(perfluoronaphthyl)borate, triphenylphosphoniumtetra( pentafluorophenyl)borate, triphenylphosphonium tetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(2,6-difluorophenyl) Borate, triphenylphosphonium tetra(perfluoronaphthyl)borate, trimethylammoniumtetra(2,6-ditrifluoromethylphenyl)borate, triethylammoniumtetra(pentafluorophenyl)borate, triethylammoniumtetra(2,6-ditrifluoromethylphenyl) ) borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tripropylammonium tetra(perfluoronaphthyl)borate , tripropylammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate, and the like.

Among these, tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, and tributylammonium tetra(perfluoromethylphenyl)borate. naphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate, dimethylanilinium Tetra(perfluoronaphthyl)borate is preferred.

Further, a second example of the borate compound is represented by the following general formula.
[L2] ⁺ [B(R2)(R3)(X4)(X5)] ^-
In the general formula, L2 is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, t-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton Examples include. Furthermore, R2, R3, X4 and X5 are as defined above.

Specific examples of the above compounds include trityltetraphenylborate, trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate, trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate, Trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoro methylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenylborate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p- tolyl)borate, tropinium tetra(m-tolyl)borate, tropiniumtetra(o-fluorophenyl)borate, tropiniumtetra(p-fluorophenyl)borate, tropiniumtetra(m-fluorophenyl)borate, tropiniumtetra (3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, Tropinium tetra(perfluoronaphthyl)borate, NaBPh ₄ , NaB(o-CH ₃ -Ph) ₄ , NaB(p-CH ₃ -Ph) ₄ , NaB(m-CH ₃ -Ph) ₄ , NaB(o- F-Ph) ₄ , NaB(p-F-Ph) ₄ , NaB(m-F-Ph) ₄ , NaB(3,5-F ₂ -Ph) ₄ , NaB(C ₆ F ₃ ) ₄ , NaB( 2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HBPh _4.2 diethyl ether, HB(3, 5-F ₂ -Ph) _4.2 diethyl ether, HB(C ₆ F ₅ ) _4.2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether, HB(3, Examples include 5-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether and HB(C ₁₀ H ₇ ) _4.2 diethyl ether.

Among these, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, Tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB(C ₆ F ₃ ) ₄ , NaB(2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HB(C ₆ F ₅ ) _4.2 diethyl ether, HB(2,6-(CF ₃ ) ₂ -Ph) _4.2 diethyl ether, HB(3,5-(CF ₃ ) ₂ -Ph) _4.2 Diethyl ether and HB(C ₁₀ H ₇ ) _4.2 diethyl ether are preferred.

More preferably, among these, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(pentafluorophenyl)borate, and tropiniumtetra(2,6-ditrifluoromethylphenyl)borate. methylphenyl)borate, NaB(C ₆ F ₃ ) ₄ , NaB(2,6-(CF ₃ ) ₂ -Ph) ₄ , HB(C ₆ F ₅ ) _4.2 diethyl ether, HB(2,6-( Examples include CF ₃ ) ₂ -Ph) _{4.2 diethyl} ether, HB(3,5-(CF ₃ ) ₂ -Ph) 4.2 diethyl ether, and HB(C ₁₀ H ₇ ) _4.2 diethyl ether.

Among the compound groups exemplified above, component (B) is preferably an aluminoxane or a boron compound.

(2) Ion-exchange layered silicate Further, as a specific example of component (B), ion-exchange layered silicate (hereinafter, sometimes simply abbreviated as "silicate") may be mentioned. An ion-exchangeable layered silicate is a silicate compound that has a crystal structure in which surfaces formed by ionic bonds are stacked in parallel with each other due to bonding force, and the ions contained therein can be exchanged. Various types of silicates are known, and are specifically described in Haruo Shiramizu, "Clay Mineralogy", Asakura Shoten (1995).
In the present invention, those preferably used as the ion-exchanged layered silicate of component (B) belong to the smectite group, and specifically, montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, and stevensite. etc. can be mentioned. Among them, montmorillonite is preferred from the viewpoint of increasing the polymerization activity and molecular weight of the copolymer portion.

Since most silicates are produced in nature as the main component of clay minerals, they often contain impurities other than ion-exchanged layered silicates (such as quartz and cristobalite). The smectite group silicate used may contain impurities.
The silicate may be subjected to acid treatment and/or salt treatment. In this treatment, the treatment may be performed by mixing the corresponding acid and base to generate a salt in the reaction system.

As component (B), a mixture of the above-mentioned organoaluminumoxy compound, a borane compound, a borate compound, or an ion-exchanged layered silicate can also be used. Furthermore, each may be used alone or two or more types may be used.

<Third component>
Yet another embodiment of the present invention contains an alkyl aluminum compound as component (C) in addition to the components (A) and (B). An example of the alkyl aluminum compound used as component (C) is represented by the following general formula.
Al(R4) _a X _(3-a)
In the general formula, R4 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and less than or equal to 3.
Specific examples of organoaluminum compounds represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum, halogen- or alkoxy-containing such as diethylaluminum monochloride, diethylaluminium monomethoxide, etc. Examples include aluminum alkyl.

Among these, triisobutylaluminum is preferred. Furthermore, two or more of the above organoaluminum compounds may be used in combination. Further, the above aluminum compound may be modified with alcohol, phenol, etc. and used. Examples of these modifiers include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, 2,6-di-t-butylphenol, and preferred specific examples include 2,6-dimethylphenol and 2,6-di-t-butylphenol. -dimethylphenol, 2,6-di-t-butylphenol.

<Method for preparing catalyst composition>
In the method for preparing the catalyst composition for olefin polymerization according to the present invention, for example, a method is used in which component (A) is brought into contact with (B) and (C) as necessary. In the case of a catalyst composition containing two components (A) and (B), the two may be prepared by mixing them in advance, or the other component may be added to a polymerization system in which one of the components is present. It may also be prepared by In the case of a catalyst composition containing three components (A), (B), and (C), the specific method such as the order of contacting each component is not particularly limited, but the following methods can be exemplified. .
(i) Method of adding component (C) after contacting component (A) and component (B) (ii) Adding component (B) after bringing component (A) and component (C) into contact (iii) Method of adding component (A) after contacting component (B) and component (C) (iv) Method of adding component (A), (B), and (C) at the same time How to do it.
Furthermore, different types of components may be used as a mixture in each component, or may be contacted separately in different orders. Note that this contact may be carried out not only during catalyst preparation but also during prepolymerization with olefin or during olefin polymerization. Alternatively, the components may be divided and brought into contact with each component, such as by contacting component (B) with component (C) and then adding a mixture of component (A) and component (C).

It is preferable that the above-mentioned components (A), (B), and (C) be contacted in an inert gas such as nitrogen and an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene. The contacting can be carried out at a temperature between -20°C and the boiling point of the solvent, particularly preferably at a temperature between room temperature and the boiling point of the solvent.

<Polymerization method>
(1) Monomer The above catalyst for olefin polymerization can be used for homopolymerization of α-olefins or copolymerization of two or more types of α-olefins. α-olefins include those having 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, and specifically include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1 - Examples include pentene. More preferred are ethylene and propylene. It is also possible to copolymerize two or more types of α-olefins. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. Of course, it is also possible to use small amounts of comonomers other than α-olefins, and in this case, styrenes such as styrene, 4-methylstyrene, 4-dimethylaminostyrene, 1,4-butadiene, 1,5-hexadiene, Examples include compounds having polymerizable double bonds such as dienes such as 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, and oxygen-containing compounds such as hexenol, hexenoic acid, and methyl octenoate. I can do it.

(2) Polymerization method The polymerization reaction can be carried out in the presence of a catalyst, preferably by slurry polymerization, bulk polymerization, or gas phase polymerization. In the case of slurry polymerization, aliphatic hydrocarbons such as isobutane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic polymers such as cyclohexane and methylcyclohexane are Ethylene or the like is polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons. Another preferred embodiment is bulk polymerization in which a liquid monomer such as liquid ethylene or liquid propylene is also used as a solvent.

The polymerization conditions include a temperature of 0 to 250°C, preferably 20 to 110°C, more preferably 60 to 100°C, and a pressure of normal pressure to 10 MPa, preferably normal pressure to 4 MPa, more preferably 0.5 to 2 MPa. The polymerization time is usually in the range of 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

A component for the purpose of removing water, a so-called scavenger, may be added to the polymerization system without any problem. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminium, the above-mentioned organoaluminumoxy compounds, modified organoaluminum compounds containing branched alkyl, diethylzinc, and dibutylzinc. Organic zinc compounds such as diethylmagnesium, dibutylmagnesium, ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride are used.
Among these, triethylaluminum, triisobutylaluminum, ethylbutylmagnesium, and tri-n-octylaluminum are preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

The catalyst or catalyst composition of the present invention can be applied without any problem to a multi-stage polymerization system including two or more stages in which the polymerization conditions are different from each other.

In the following, the present invention will be specifically explained with reference to examples, and the rationality and significance of the configuration of the present invention and its superiority over the prior art will be demonstrated. However, the following examples are merely illustrative, and it is obvious that the scope of the present invention is not limited only to these specific examples.

<Evaluation method>
(1) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
(Measurement conditions) Model used: Waters 150C Detector: FOXBORO MIRAN1A IR detector (measurement wavelength: 3.42 μm), measurement temperature: 140°C, solvent: orthodichlorobenzene (ODCB), column: Showa Denko AD806M/S (3 bottles), flow rate: 1.0 mL/min, injection volume: 0.2 mL
(Sample Preparation) For the sample, prepare a 1 mg/mL solution using ODCB (containing 0.5 mg/mL BHT (2,6-di-t-butyl-4-methylphenol)) and heat at 140°C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the retention capacity was converted to the molecular weight using a standard polystyrene calibration curve prepared in advance. The standard polystyrenes used are all manufactured by Tosoh Corporation and are F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve was created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL BHT) so that each concentration was 0.5 mg/mL. For the calibration curve, a cubic equation obtained by approximation using the least squares method was used. The following numerical value was used for the viscosity formula [η]=K×M ^α used for conversion to molecular weight.
PS: K=1.38×10 ⁻⁴ , α=0.7
PE: K=3.92×10 ⁻⁴ , α=0.733
PP: K=1.03×10 ⁻⁴ , α=0.78

(2) Melting point (Tm)
Using a Seiko Instruments DSC6200 differential scanning calorimeter, a sheet-shaped sample piece was packed into a 5 mg aluminum pan, heated from room temperature to 200°C at a heating rate of 100°C/min, and held for 5 minutes. Afterwards, the temperature was lowered to 20°C at a rate of 10°C/min for crystallization, and then the temperature was raised to 200°C at a rate of 10°C/min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final heating step performed to obtain the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.

(3) NMR
[Sample preparation]
200 mg of the sample was added to an NMR sample with an inner diameter of 10 mm along with 2.4 ml of o-dichlorobenzene/deuterated bromide benzene (C ₆ D ₅ Br) = 4/1 (volume ratio) and hexamethyldisiloxane, which is a reference substance for chemical shift. The mixture was placed in a tube, purged with nitrogen, sealed, and uniformly dissolved using a block heater at 150°C.
For NMR measurement, an AV400 type NMR apparatus manufactured by Bruker Japan Co., Ltd. equipped with a normal probe of 10 mm diameter was used.
The amount of ethyl branches refers to the number of ethyl branches per 1000 carbon atoms (pieces/1000C), and ¹³ C-NMR was used to quantify it. The measurement conditions for ¹³ C-NMR were a sample temperature of 120° C., a pulse angle of 45°, a pulse interval of 2.76 seconds, and the number of integrations of 75,000 or more times, using the proton broadband decoupling method.
For chemical shifts, the ¹³ C signal of hexamethyldisiloxane was set at 1.98 ppm, and the chemical shifts of other ¹³ C signals were based on this.
Method for calculating the amount of ethyl branches Using the ¹³ C-NMR spectrum obtained under the above measurement conditions, the amount of ethyl branches (pieces/1000C) was calculated from the following formula.
Amount of ethyl branches (pieces/1000C)=I(B)/4×1000/I(total)
Here, I(B) and I(total) are quantities expressed by the following formulas. Further, the correction coefficients 1 to 10 are shown in Table 1.
I (B) = I _{39.71 to 39.68} × correction coefficient 10 + I _{33.86 to 33.83} × correction coefficient 9
+I _{11.16 to 11.13} × correction coefficient 1

I (total) = I (B) + I _{13.96 to 13.90} × correction coefficient 2
+I _{22.73 to 22,69} × correction coefficient 3
+I _{26.58 to 26.50} × correction coefficient 4
+I _27.30~22.25 × correction coefficient 5
+I _{31.48 to 27.39} × correction coefficient 6
+I _{32.06 to 32.02} × correction coefficient 7
+I _{33.77 to 33.75} × correction coefficient 8

上記各々の式においてＩは積分強度を、Ｉの下つき添字の数値は化学シフトの範囲を示す。例えばＩ_{３９．７１～３９．６８}は３９．７１ｐｐｍと３９．６８ｐｐｍの間に検出したポリマー由来の^１３Ｃシグナルの積分強度を示す。

In each of the above formulas, I represents the integrated intensity, and the subscript number of I represents the range of chemical shift. For example, I _39.71-39.68 indicates the integrated intensity of the ¹³ C signal derived from the polymer detected between 39.71 ppm and 39.68 ppm.

The synthesis route of the transition metal complex in the present invention is shown below. In the following synthesis examples, unless otherwise specified, the operations were performed under an inert gas atmosphere, and the solvent used was one that had been dehydrated and deoxidized.

工程１：３，６－ジフェニルカルバゾールの合成
３，６－ジヨードカルバゾール６．２６g(15mmol)、水２０ml、ジメトキシエタン１２０mLの溶液に、フェニルボロン酸５．４７g(45mmol)、酢酸パラジウム１６７mg(0.7mmol)トリ(o-トリル)ホスフィン４５４mg(1.5mmol)、水酸化バリウム７．６８g(45mmol)を順次加え、８０℃で１２時間加熱した。反応物を濃縮しジクロロメタンを加えて水洗した。有機層を、硫酸ナトリウムで乾燥後、減圧乾固した。その後、石油エーテルで洗浄し、３，６－ジフェニルカルバゾールの粗精製物を黄色固体として４．８g得た。 [Example 1]
(1-1) (N,N,N)-(1,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazolate) iron dichloride (complex A) synthesis

Step 1: Synthesis of 3,6-diphenylcarbazole To a solution of 6.26 g (15 mmol) of 3,6-diiodocarbazole, 20 ml of water, and 120 ml of dimethoxyethane, 5.47 g (45 mmol) of phenylboronic acid and 167 mg (0.7 mg) of palladium acetate were added. 454 mg (1.5 mmol) of tri(o-tolyl)phosphine and 7.68 g (45 mmol) of barium hydroxide were sequentially added, and the mixture was heated at 80° C. for 12 hours. The reaction mixture was concentrated, dichloromethane was added, and the mixture was washed with water. The organic layer was dried over sodium sulfate and then dried under reduced pressure. Thereafter, the mixture was washed with petroleum ether to obtain 4.8 g of crudely purified 3,6-diphenylcarbazole as a yellow solid.

Step 2: Synthesis of 1,8-dibromo-3,6-diphenyl-carbazole To a solution of 2.00 g (6.26 mmol) of 3,6-diphenylcarbazole in 20 ml of acetic acid, 2.20 g of bromine was added dropwise at 20°C. The mixture was stirred as it was for 12 hours. The reaction solution was poured into a sodium hydrogen carbonate solution and extracted with dichloromethane. The organic layer was washed with a sodium carbonate solution and a sodium chloride solution, dried over sodium sulfate, and evaporated to dryness. After washing with a dichloromethane/petroleum ether mixture, 2.0 g of a crude product of 1,8-dibromo-3,6-diphenyl-carbazole was obtained as a yellow solid.

Step 3: Synthesis of 1,8-dicyano-3,6-diphenyl-carbazole 4.0 g (8.4 mmol) of crude product of 1,8-dibromo-3,6-diphenyl-carbazole and 50 ml of N,N-dimethylformamide 2.25 g (25.2 mmol) of copper cyanide was added to the solution and stirred at 130°C for 12 hours. The reaction solution was poured into aqueous ammonia, and solids were filtered off. The solid was dissolved in dichloromethane, washed with aqueous ammonia and aqueous sodium chloride, dried over sodium sulfate, concentrated, the precipitated solid was filtered, and 1.8 g of 1,8-dicyano-3,6-diphenyl-carbazole was dissolved in yellow. Obtained as a solid.

Step 4: Synthesis of 1,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazole 1.8 g (4.9 mmol) of 1,8-dicyano-3,6-diphenyl-carbazole 2.66 g (19.5 mmol) of zinc chloride and 2.67 g (19.5 mmol) of 2-amino-2-phenylethanol were added to a solution of 20 mL of chlorobenzene. Thereafter, the mixture was stirred at 130°C for 36 hours.
After cooling, the reaction solution was added to an aqueous ethylenediamine solution, extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate and dried under reduced pressure. Purification was performed using a silica gel column to obtain 0.25 g (yield: 8.4%) of 1,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazole as a colorless solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ4.30(t,2H), δ4.96(t,2H), δ5.62(t,2H), δ7.09~7.86(br,20H), δ8 .21(s,2H),δ8.98(s,2H),δ12.1(s,1H).

Step 5: Synthesis of (N,N,N)-(1,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazolate) iron dichloride (complex A) 1 ,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazole 1.95g (3.2mmol), iron(II) chloride 0.41g (3.2mmol), and tetrahydrofuran 20ml were mixed. The mixture was heated under reflux for 6.5 hours. Thereafter, the mixture was heated and stirred in air at 60° C. for 3 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. Recrystallize from dichloromethane/hexane to obtain (N,N,N)-(1,8-bis(4-phenyl-4,5-dihydroxazolyl)-3,6-diphenylcarbazolate) black iron dichloride. 2.1 g (yield: 89%) of green crystals were obtained.

(1-2) Ethylene polymerization using complex A (pre-contact method)
25 mg of Complex A was dissolved in 10 mL of toluene, 20 mL of MMAO-3A/hexane solution (Al = 5.9 wt%, manufactured by Tosoh Fine-Chem) was added thereto, and the mixture was stirred for 5 minutes to prepare a complex solution.
790 mL of toluene was introduced into a stirred autoclave having an internal volume of 3 L, and then 20 mL of MMAO-3A/hexane solution was added. The inside of the reactor was replaced with ethylene, and the temperature was raised to 80°C. The pressure was increased to 2.5 MPa with ethylene. The previously prepared complex solution was injected therein with N ₂ . After maintaining the ethylene pressure at 2.5 MPa for 30 minutes, ethanol was injected under pressure to stop the polymerization.
The obtained slurry was poured into hydrochloric acid/ethanol, filtered, washed with ethanol, and dried to obtain 0.57 g of polymer. The activity of the catalyst is 33,500 (g-PE/mol-Fe/h), the obtained polymer has a molecular weight (Mw) = 1,048,000, a molecular weight distribution (Mw/Mn) = 3.1, and a melting point of 136. The temperature was .7 (°C). The number of Me branches determined by NMR was below the detection limit (0.1 pieces/1000 C or less).
The polymerization results are listed in Table 2.

[Example 2]
Ethylene polymerization using complex A (reactor addition method)
A complex solution was prepared by dissolving 25 mg of Complex A in 10 mL of toluene.
790 mL of toluene was introduced into a stirred autoclave with an internal volume of 3 L, and then 20 mL of MAO/toluene solution (Al=20 wt%, manufactured by Nippon Alkyla Aluminum Co., Ltd.) was added. The inside of the reactor was replaced with ethylene, and the temperature was raised to 80°C. The pressure was increased to 2.5 MPa with ethylene. The previously prepared complex solution was injected therein with N ₂ . After maintaining the ethylene pressure at 2.5 MPa for 60 minutes, ethanol was injected under pressure to stop the polymerization.
The obtained slurry was poured into hydrochloric acid/ethanol, filtered, washed with ethanol, and dried to obtain 0.6 g of polymer. The activity of the catalyst is 35,300 (g-PE/mol-Fe/h), the obtained polymer has a molecular weight (Mw) = 1,206,000, a molecular weight distribution (Mw/Mn) = 3.1, and a melting point of 136. .6 (°C). The number of Me branches determined by NMR was below the detection limit (0.1 or less/1000C).
The polymerization results are listed in Table 2.

工程１：（イソインドール－１，３－ジイリデン）ビス（酢酸エチル）の合成
フタルイミド１０ｇ（６８mmol）及び(トリフェニルホスホラニリデン)酢酸エチル １１８ｇ（３４０mmol）を混合した。混合物を１４０℃で２４時間加熱した。反応混合をシリカゲルカラムで精製し、（イソインドール－１，３－ジイリデン）ビス（酢酸エチル）４．７ｇ(収率２４％)を得た。
^１H-NMR(400MHz,CDCl₃):δ1.36(t,6H),δ4.29(q,4H),δ5.64(s,2H),δ7.53(m,2H),δ7.69(m,2H),δ11.50(br,2H). [Example 3]
(3-1) Synthesis of (N,N,N)-(1,3-bis((4-phenyl-4,5-dihydroxazolyl)methylene)isoindolate)iron dichloride (complex B)

Step 1: Synthesis of (isoindole-1,3-diylidene)bis(ethyl acetate) 10 g (68 mmol) of phthalimide and 118 g (340 mmol) of ethyl (triphenylphosphoranylidene) acetate were mixed. The mixture was heated at 140°C for 24 hours. The reaction mixture was purified using a silica gel column to obtain 4.7 g (yield 24%) of (isoindole-1,3-diylidene)bis(ethyl acetate).
¹ H-NMR (400MHz, CDCl ₃ ): δ1.36(t,6H), δ4.29(q,4H), δ5.64(s,2H), δ7.53(m,2H), δ7.69 (m,2H),δ11.50(br,2H).

Step 2: Synthesis of (isoindole-1,3-diylidene)bis(N-(2-hydroxy-1-phenylethyl)-acetamide) 10.3 g of isoindole-1,3-diylidene)bis(ethyl acetate) 36 mmol) and 24.6 g (180 mmol) of (R)-2-amino-2-phenylethanol were mixed. The solid mixture was then heated to 120°C. 290 mg (7.2 mmol) of sodium hydride was added to the resulting mixture, and the reaction mixture was stirred for 12 hours.
The reaction was poured into water and extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified with a silica gel column to obtain 5.7 g (yield 34%) of (isoindole-1,3-diylidene)bis(N-(2-hydroxy-1-phenylethyl)-acetamide).

Step 3: Synthesis of 1,3-bis((4,5-dihydro-4-phenyl-2-oxazolyl)methylene)-2,3-dihydro-1H-isoindole 4.08 g of (diethylamino)sulfur trifluoride ( 25.3 mmol) was added to a solution of 5.4 g (11.50 mmol) of (isoindole-1,3-diylidene)bis(N-(2-hydroxy-1-phenylethyl)-acetamide) in 200 ml of dichloromethane at 0°C. . Thereafter, the mixture was stirred at 0°C for 1 hour, and 4.8 g (34 mmol) of potassium carbonate was added. The resulting mixture was stirred at room temperature for 12 hours. The reaction was poured into 200 mL of saturated sodium bicarbonate solution. Then, it was extracted with dichloromethane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified with an alumina column to give 1.9 g of 1,3-bis((4,5-dihydro-4-phenyl-2-oxazolyl)methylene)-2,3-dihydro-1H-isoindole (yield 39%) was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ4.08(t,2H), δ4.66(t,2H), δ5.31(t,2H), δ5.73(s,2H), δ7.22 (m,2H),δ7.31(m,8H),δ7.51(dd,2H),δ7.72(dd,2H),δ11.90(br,1H).

Step 4: Synthesis of (N,N,N)-(1,3-bis((4-phenyl-4,5-dihydroxazolyl)methylene)isoindolate)iron dichloride (complex B) 1,3- Bis((4,5-dihydro-4-phenyl-2-oxazolyl)methylene)-2,3-dihydro-1H-isoindole 1.0 g (2.3 mmol), iron(II) chloride 0.29 g (2. 3 mmol) and 15 ml of tetrahydrofuran were mixed and heated under reflux for 3 hours. Thereafter, the mixture was heated and stirred in air at 60° C. for 3 hours. After cooling, the reaction solution was filtered through Celite, and the solvent of the filtrate was distilled off under reduced pressure. Recrystallize from dichloromethane/hexane to obtain ((N,N,N)-(1,3-bis((4-phenyl-4,5-dihydroxazolyl)methylene)isoindolate)iron dichloride (complex B). 0.26 g (yield 19%) of black brown crystals were obtained.

(3-2) Ethylene polymerization using complex B (pre-contact method)
20 mg of Complex B was dissolved in 10 mL of toluene, 20 mL of MMAO-3A/hexane solution (Al = 5.9 wt%, manufactured by Tosoh Fine-Chem) was added thereto, and the mixture was stirred for 5 minutes to prepare a complex solution.
790 mL of toluene was introduced into a stirred autoclave having an internal volume of 3 L, and then 20 mL of MMAO-3A/hexane solution was added. The inside of the reactor was replaced with ethylene, and the temperature was raised to 80°C. The pressure was increased to 2.5 MPa with ethylene. The previously prepared complex solution was injected therein with N ₂ . After maintaining the ethylene pressure at 2.5 MPa for 30 minutes, ethanol was injected under pressure to stop the polymerization.
The obtained slurry was poured into hydrochloric acid/ethanol, filtered, washed with ethanol, and dried to obtain 2.47 g of polymer. The activity of the catalyst is 136,000 (g-PE/mol-Fe/h), the obtained polymer has a molecular weight (Mw) = 266,000, a molecular weight distribution (Mw/Mn) = 2.2, and a melting point of 135.2. (°C). The number of Me branches determined by NMR was below the detection limit (0.1 pieces/1000 C or less).
The polymerization results are listed in Table 2.

As is clear from Table 2, the catalyst or catalyst composition of the present invention is useful as a polyethylene polymerization catalyst. In particular, the obtained polyethylene has a very high melting point, very little branching of methyl groups, high density, and excellent mechanical properties.

That is, the catalyst or catalyst composition of the present invention is a catalyst that enables the production of polyolefins with excellent properties, and is therefore very useful in polyolefin production and application fields such as film forming.

Claims (15)

An α-olefin polymerization catalyst characterized by containing a transition metal complex represented by the following general formula (1 a ).

[In formula (1 a ),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^d are each independently a hydrogen atom, a halogen atom , a hydrocarbon group having 1 to 30 carbon atoms, or a halogen atom-substituted group having 1 to 30 carbon atoms; 30 hydrocarbon groups, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms ;
Z ¹ and Z ² are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms which may contain an unsaturated bond , and the hydrocarbon group is R ^1' (where R ^1' may be substituted with one or more substituents represented by (synonymous with R ¹ ),
At two points in Z ¹ and two points in Z ² , one or more methylene groups (-CH ₂ -) are O, S, or NR ^e (R ^e is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. The group may be connected by a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms, and may be substituted with a saturated or unsaturated ring. The ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group,
R ²⁰ and R ²¹ are not present,
M represents an iron metal atom;
Q represents an oxygen atom , and the cyclic structure containing Q may contain an unsaturated bond,
Y is a nitrogen atom ,
n is 2 ,
m is 1 ,
p is 0 ,
X represents a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms and a halogen , and Z ³ and Z ⁴ may each independently contain an unsaturated bond, Indicates a hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms in which one or more methylene groups (-CH ₂ -) other than the terminal may be replaced with O, S or NR ^e , and the hydrocarbon group is It may be substituted with one or more substituents represented by R ^1' (where R ^1' has the same meaning as R ¹ ), or
Z ¹ and Z ³ , Z ² and Z ⁴ , and Z ³ and Z ⁴ may be connected to each other to form a carbocyclic or heterocyclic ring structure that may contain an unsaturated bond. , the ring may be substituted with one or more substituents represented by R ^1' (where R ^1' is the same as R ¹ ), and the ring may be an alicyclic group, a heterocyclic group, Alternatively, the aromatic group may be further condensed,
The five-membered ring having Z ¹ , Z ² , Z ³ , and Z ⁴ and containing Y may contain an unsaturated bond. ] Said Z ¹ and Z ² is a methylene group, and Z ¹ are Y and Z ¹ An unsaturated bond may be formed with the carbon atom adjacent to Z. ² are Y and Z ² may form an unsaturated bond with the carbon atom adjacent to R, and the methylene group ^1' (Here R ^1' is, R ¹ The α-olefin polymerization catalyst according to claim 1, which may be substituted with a substituent represented by (synonymous with). Said Z ³ and Z ⁴ each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (Here R ^1’ is, R ¹ may be substituted with one or more substituents shown in (synonymous with), or
Z ¹ and Z ³ ,Z ² and Z ⁴ ,Z ³ and Z ⁴ may be connected to each other to form a 6-membered carbocyclic ring structure that may contain an unsaturated bond, and the ring is R ^1’ (Here R ^1’ is, R ¹ may be substituted with one or more substituents represented by (synonymous with), and the ring may be further fused with an alicyclic or aromatic group,
Z ¹ ,Z ² ,Z ³ ,Z ⁴ The α-olefin polymerization catalyst according to claim 1 or 2, wherein the five-membered ring containing Y may contain an unsaturated bond. Said R ^1' The α-olefin polymerization catalyst according to any one of claims 1 to 3, wherein is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The α-olefin polymerization catalyst according to any one of claims 1 to 4, wherein the transition metal complex is a transition metal complex represented by the following general formula (1b).

[In formula (1b),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined in claim 1,
R ³ to R ⁷ and R ¹³ to R ¹⁷ are each independently synonymous with R ¹ , or the pairs of R ³ and R ⁷ , R ⁷ and R ¹⁷ , and R ¹⁷ and R ¹³ are each They may be joined together by a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring, and the ring may be an alicyclic or may further be fused with an aromatic group. ] The α-olefin polymerization catalyst according to any one of claims 1 to 5, wherein the transition metal complex is a transition metal complex represented by the following general formula (1c).

[In formula (1c),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , R ²⁰ , R ²¹ , M, Q, Y, n, m, p, and X are as defined in claim 1,
R ³ , R ⁷ , R ¹³ and R ¹⁷ are each independently synonymous with R ¹ or
R ³ and R ⁷ and/or R ¹³ and R ¹⁷ are each connected together via a linear or branched hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring. The ring may be further fused with an alicyclic group, a heterocyclic group, or an aromatic group,
the below described:

At least one of the bonds included in the structure shown by , excluding the bond containing Y, forms a double bond. ] The α-olefin polymerization catalyst according to any one of claims 1 to 6, wherein the transition metal complex is a transition metal complex represented by the following general formula (1d).

[In formula (1d),
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^e , M, n, and X are as defined in claim 1,
R ³¹ to R ³³ and R ⁴¹ to R ⁴³ each independently represent a hydrogen atom, a halogen atom, or one or more methylene groups other than the terminal (-CH ₂ -) replaced with O, S, or NR ^e . a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and a hydrocarbon group having 1 to 30 carbon atoms, which may be substituted with an alkoxy group; 30 represents a substituent selected from the group consisting of a silyl group substituted with a hydrocarbon group. ] Said R ¹ ,R ² ,R ¹¹ ,R ¹² ,R ^a ～R ^d each independently represents a hydrogen atom, an aryl group having 6 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms substituted with a halogen atom. The α-olefin polymerization catalyst described in . Said R ³ ,R ⁷ ,R ¹³ and R ¹⁷ In R ³ and R ⁷ and R ¹⁷ and R ¹³ are connected together by a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring, and the ring is an alicyclic ring. The α-olefin polymerization catalyst according to claim 5 or 6, characterized in that the group or aromatic group may be further condensed. Said R ⁷ and R ¹⁷ are connected together by a linear or branched divalent hydrocarbon group having 1 to 30 carbon atoms to form a saturated or unsaturated ring, and the ring is an alicyclic or aromatic ring. The α-olefin polymerization catalyst according to any one of claims 5, 6, and 9, wherein the group group may be further condensed. Said R ¹ ,R ² ,R ¹¹ ,R ¹² ,R ^a ～R ^d are each independently a hydrogen atom or an aryl group having 6 to 14 carbon atoms, and R ¹ and R ¹¹ When is other than a hydrogen atom, R ² and R ¹² is a hydrogen atom, and R ² and R ¹² When is other than a hydrogen atom, R ¹ and R ¹¹ The α-olefin polymerization catalyst according to any one of claims 1 to 10, wherein is a hydrogen atom. Component (A): the transition metal complex according to any one of claims 1 to 11, and component (B): a compound or ion-exchangeable layered silicate that reacts with the transition metal complex to form an ion pair. A catalyst composition for α-olefin polymerization, comprising: The catalyst composition for α-olefin polymerization according to claim 12, wherein the component (B) is an aluminoxane or a boron compound. The catalyst composition for α-olefin polymerization according to claim 12 or 13, further comprising the following component (C).
Component (C): Alkylaluminium compound Polymerizing an α-olefin using the α-olefin polymerization catalyst according to any one of claims 1 to 11 or the α-olefin polymerization catalyst composition according to any one of claims 12 to 14. A method for producing an α-olefin polymer, the method comprising: