JP7042122B2 - Olefin polymerization catalyst - Google Patents

Description

The present invention relates to a novel catalyst composition containing a complex having a specific structure, and more particularly, to a catalyst composition containing a complex consisting of a tridentate ligand having a heterocyclic structure containing nitrogen as an essential component. , It relates to olefin polymerization.

Among resin materials, olefin polymers are excellent in various properties such as physical properties and moldability, and are highly economical and environmentally friendly, and are extremely versatile and important industrial materials.
However, since the olefin polymer does not have a polar group, it is difficult to apply it to applications that require physical properties such as adhesiveness to other materials, printability, or compatibility with fillers. There are also many. In particular, polyethylene resin is derived from short-chain branching such as methyl branching, and its density decreases and its mechanical properties are inferior. Not only when it is used alone, but also when it is used as a composition with other resins. , Its application range is limited.

In order to solve these problems, in recent years, development of a so-called post-metallocene, a late-period transition metal complex catalyst, and control of the physical properties of an olefin polymer have been carried out. As the post-metallocene catalyst for olefin polymerization, for example, an iron catalyst such as a tridentate iron complex having a diiminopyridine skeleton and bisaryliminopyridine iron is used, and the result of ethylene polymerization by these catalysts is known (). Patent Documents 1 to 3 and Non-Patent Documents 1).

Special Table 2006-501067 Gazette Japanese Patent No. 4108141 Special Table 2002-513823 Gazette

Organometallics, 2005, 24, 4878-4881

Ethylene polymerization using an iron complex has been reported as described above, but in Patent Document 1, it is essential to add a zinc compound in order to reduce short chain branching, and in the case of polymerization without addition. , Methyl branch has many values. Further, in Non-Patent Document 1, the obtained polyethylene used MMAO had 9 to 17 methyl branches / 1000C, and no satisfactory polyethylene was obtained. Patent Document 3 also evaluates PP polymerization, but the details of the obtained polymer are unknown. As described above, it is desired to develop a catalyst capable of controlling the generation of branching in olefin polymerization and producing a polyolefin having excellent various properties, particularly polyethylene having few methyl branches.

An object of the present invention is to create a catalyst composition that functions effectively as an olefin polymerization catalyst. As a result of diligent studies aimed at solving the above-mentioned problems, the present inventors have found that a composition containing a specific iron complex functions as a component of a polymerization catalyst suitable for the above-mentioned purpose. It came to be created.

［式中、
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、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し、
Ｚ^１及びＺ^２は、各々独立して、不飽和結合を含んでいてもよい炭素数２～３０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、
Ｒ^２０、Ｒ^２１は、各々独立して、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、酸素若しくは窒素を含む炭素数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 composition constituting the basic invention (first invention) of the present invention is a catalyst composition for α-olefin polymerization, which comprises a transition metal complex represented by the following general formula (1). ..

[During the ceremony,
R ¹ , R ² , R ¹¹ , R ¹² , R ^a to R ^d are independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a halogen atom having 1 to 1 carbon atoms. The substituents selected from the group consisting of 30 hydrocarbon groups, 2 to 30 carbon hydrocarbon groups substituted with alkoxy groups, and silyl groups substituted with 1 to 30 carbon carbon groups are shown.
Z ¹ and Z ² are each independently a divalent hydrocarbon group having 2 to 30 carbon atoms which may contain an unsaturated bond, and the hydrocarbon group is R ^1' (here R ¹ '). ^' Is synonymous with ^R1 ) and may be substituted with one or more substituents.
R ²⁰ and R ²¹ each independently have a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and 2 to 30 carbon atoms substituted with an alkoxy group. Indicates 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.
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 an unsaturated bond may be contained in the cyclic structure containing Q.
Y is a nitrogen atom or a phosphorus atom,
n is 1 or 2
m is an integer from 1 to 3 and
p is 0 or 1 and is
X is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. A substituent selected from the group consisting of 10 acyl groups, 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. Is shown. ]

With the catalyst composition of the present invention, it is possible to efficiently produce various olefin-based polymers, particularly ethylene polymers having a small amount of branching. The catalyst composition for polyolefin polymerization using the metal complex of the present invention and the olefin polymerization method using the same are very useful from an industrial point of view.

Hereinafter, the catalyst composition of the present invention and a method for producing an olefin polymer using the same will be described in detail for each item.

<Transition metal complex>
(1) Basic Structure The catalyst composition in the present invention contains a transition metal complex having a tridentate ligand represented by the general formula (1). Here, the tridentate ligand has a heterocyclic ring-containing compound having a ring structure having a set of heteroatoms selected from the group consisting of two nitrogens, nitrogen and oxygen, nitrogen and sulfur at two positions. Is. The type of ring structure is not particularly limited as long as the set of heteroatoms is a 5- to 7-membered ring existing via one carbon atom. One of the nitrogen atoms may form a double bond with an adjacent carbon atom. Non-limiting groups of such ring structures include dihydrooxazolyl groups, oxazolyl groups, dihydro-1,3-oxadinyl groups, tetrahydro-1,3-oxazepinyl groups (above the combination of nitrogen and oxygen); dihydroimidazolyl. Group, tetrahydropyrimidinyl group, hexahydropyrimidinyl group (above two nitrogens); dihydrothiazolyl group, dihydro1,3-thiazinyl group, tetrahydro-1,3-thiazepinyl group (above combination of nitrogen and sulfur) and the like. Be done.

"Hydrocarbon group" means a structure consisting of a carbon skeleton having a specified number of carbon atoms, a linear or branched alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, It includes a structure in which two or more of these groups are bonded, such as a cycloalkynyl group, an aryl group, benzyl and biphenyl. Further, in the present specification, the "hydrocarbon group" usually refers to a monovalent group, but when it is specified that the "hydrocarbon group" has a valence of divalent or higher, the "hydrocarbon group" is the above-mentioned group or It is shown that the structure has at least one hydrogen atom in the structure replaced by 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 and 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, Decahydronaphthyl group, mentyl group, neomentyl group, neopentyl group, 5-decyl group and the like. Among these, preferred substituents are an isopropyl group, an isobutyl group and a 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 anthrasenyl group and a fluorenyl group, and a substituent may be present in the aromatic ring of these aryl groups. Examples of the substituents that may be present are an alkyl group, an aryl group, a fusion aryl group, a phenylcyclohexyl group, a phenylbutenyl group, a trill group, a xsilyl group, a p-ethylphenyl group and the like. Among these, preferable aryl groups are a phenyl group and a substituted phenyl group, and preferred specific examples of the substituent of the substituted phenyl group are a methyl group, an ethyl group and a phenyl group, and further particularly preferably. It is a methyl group.

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

The "alkoxy group" means a hydrocarbon group having an oxygen atom bonded to the terminal, wherein the oxygen is not bonded to the aromatic ring. An alkoxy group having 1 to 4 carbon atoms is preferable, and specific examples thereof are a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, a t-butoxy group and the like. Among these, a more preferable substituent is a methoxy group, an ethoxy group or an isopropoxy group, and a particularly preferable group is a methoxy group.

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 a methoxymethyl group or a methoxyethyl group.

The "silyl group" means a substituent having a silicon terminal, and the silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms is preferably a silyl group having 3 to 18 carbon atoms, which is preferable. Examples are a trimethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylphenylsilyl group, and a triphenylsilyl group. Among these, a more preferable substituent is a trimethylsilyl group or a dimethylphenylsilyl group, and particularly preferably a trimethylsilyl group.

X is a monovalent group bonded to the central metal, which is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, an alkoxy group having 1 to 10 carbon atoms, and carbon. An aryloxy group having 6 to 20 carbon atoms, 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, and a substituted amino group having 1 to 12 carbon atoms. , The substituents selected from the group consisting of halogens are shown.

"Contains oxygen or nitrogen" means that one or more methylene groups ( _-CH2- ) other than the terminal of the hydrocarbon group have been replaced by oxygen or nitrogen. However, two or more adjacent carbon atoms are not replaced. When replaced with nitrogen, 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 preferred specific examples thereof are a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a preferred specific example. It is a t-butoxy group or the like. Among these, a more preferable substituent is a methoxy group, an ethoxy group or an isopropoxy group, and a particularly preferable group is a methoxy group.

The allyloxy group having 6 to 20 carbon atoms is preferably an allyloxy group having 6 to 12 carbon atoms, and preferred specific examples thereof are a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, and a 2,6-dimethylphenoxy group. Groups include 3,5-di-t-butylphenoxy groups and 2,6-di-t-butylphenoxy groups. Among these, more preferable substituents are a phenoxy group, a 3,5-di-t-butylphenoxy group or a 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group and a 3,5-di-. 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 preferred specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutylyl group, a valeryl group, an isovaleryl group and a pivaloyl group. Examples include benzoyl groups. Among these, more preferable substituents are an acetyl group, a pivaloyl group and a benzoyl group, and a particularly preferable one is a 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 preferably has 2 to 9 carbon atoms. It is an acyloxy group of 8. In this case, a hydrocarbon group having 1 to 7 carbon atoms is exemplified as a preferable R.

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

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

Z ¹ and Z ² in the general formula (1) are independently divalent hydrocarbon groups having 2 to 30 carbon atoms. Z ¹ and Z ² are the linkers of heteroatoms that are structurally coordinated to the metal atoms represented by M, and the ligand portion of the transition metal complex represented by the general formula (1) is coordinated to the tridentate. It exists to be a child. From the viewpoint of ligand design, Z ¹ and Z ² may be designed so that two carbon atoms intervene between Y and the heterocycle, such as an ethylene group and a 1,2-phenylene group. preferable. One or more substituents having the same range as the definition of R ¹ may be substituted on the hydrocarbon group. Further, Z ¹ or Z ² may form a ring or may contain an unsaturated bond.

Y in the general formula (1) is a nitrogen atom or a phosphorus atom. That is, the transition metal complex represented by the general formula (1) is three heteroatoms selected from a set of three nitrogens or two nitrogens and one phosphorus, and is tridentally coordinated with the metal atom represented by M. Has a ligand. The phosphorus atom tends to have a good coordination ability to the metal atom species represented by M, but it is more preferable that Y is a nitrogen atom from the viewpoint of ease of synthesis of the entire ligand.

M represents a metal atom selected from the group consisting of group 8-10 transition metals, and specific examples thereof include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, rhenium, and platinum. Preferably, it is 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, a neutral ligand may be coordinated to M. Specifically, carbonyl, triphenylphosphine, acetonitrile, pyridine, and tetrahydrofuran can be shown.

Q represents an oxygen atom, a nitrogen atom or a sulfur atom, and specifies the type of heteroatom that the heterocycle has other than nitrogen. m is an integer that specifies 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 always has.

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

［式中、
Ｒ^１～Ｒ^４、Ｒ^１１～Ｒ^１４、Ｒ^ａ～Ｒ^ｄは、各々独立して、水素原子、ハロゲン原子、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し、
Ｒ^２０、Ｒ^２１は、各々独立して、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し、
Ｒ^３とＲ^４、及びＲ^１３とＲ^１４は、各々一緒になって、置換基を有していてもよい５～７員環の環状構造を形成していてもよく、該環状構造はヘテロ原子を含んでいてもよく、また該環状構造は、Ｒ^３、Ｒ^４、Ｒ^１３、Ｒ^１４が直接結合する炭素原子上を含めて１つ以上の不飽和結合を有していてもよく、
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、酸素若しくは窒素を含む炭素数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。］ As a further aspect of the transition metal complex represented by the general formula (1), the catalyst composition for α-olefin polymerization of the present invention may contain the transition metal complex represented by the following general formula (2). preferable.

[During the ceremony,
R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , and Ra to R ^d are independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a halogen atom and having 1 to ¹ carbon atoms. The substituents selected from the group consisting of 30 hydrocarbon groups, 2 to 30 carbon hydrocarbon groups substituted with alkoxy groups, and silyl groups substituted with 1 to 30 carbon carbon groups are shown.
R ²⁰ and R ²¹ each independently have a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and 2 to 30 carbon atoms substituted with an alkoxy group. Indicates 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.
R ³ and R ⁴ and R ¹³ and R ¹⁴ may be combined together to form a cyclic structure of a 5- to 7-membered ring which may have a substituent, the cyclic structure being hetero. It may contain an atom and the cyclic structure may have one or more unsaturated bonds, including on the carbon atom to which R ³ , R ⁴ , R ¹³ and R ¹⁴ are directly bonded.
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 an unsaturated bond may be contained in the cyclic structure containing Q.
Y is a nitrogen atom or a phosphorus atom,
n is 1 or 2
m is an integer from 1 to 3 and
p is 0 or 1 and is
X is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. A substituent selected from the group consisting of 10 acyl groups, 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. Is shown. ]

As a more preferable embodiment of the catalyst composition for α-olefin polymerization of the present invention, in the above general formula (1) or (2), Y is a nitrogen atom, Q is oxygen or sulfur, and m is 1. It is characterized by containing a certain transition metal complex.

［式中、
Ｒ^１、Ｒ^２、Ｒ^５～Ｒ^８、Ｒ^１１、Ｒ^１２、Ｒ^１５～Ｒ^１８、Ｒ^ａ～Ｒ^ｄは、各々独立して、水素原子、ハロゲン原子、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、
ｎは、１又は２であり、
Ｘは、炭素数１～２０の炭化水素基、酸素若しくは窒素を含む炭素数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。］ As a more preferable aspect, the catalyst composition for α-olefin polymerization of the present invention is characterized by containing a transition metal complex represented by the following general formula (3).

[During the ceremony,
R ¹ , R ² , R ⁵ to R ⁸ , R ¹¹ , R ¹² , R ¹⁵ to R ¹⁸ , and R ^a to R ^d are each independently a hydrocarbon atom, a halogen atom, and a hydrocarbon having 1 to 30 carbon atoms. A group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms. Indicates a substituent selected from the group consisting of
M represents a metal atom selected from the group consisting of transition metals of groups 8 to 10 of the periodic table.
n is 1 or 2
X is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. A substituent selected from the group consisting of 10 acyl groups, 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. Is shown. ]

Preferred specific examples of the transition metal complex having a tridentate ligand represented by the formula (1), (2) or (3) include the following compounds. These are examples, and it is self-evident that they are not limited to these.

<Synthesis of metal complex>
(1) Basic synthesis route The synthesis of the transition metal complex represented by the general formula (1) can be carried out by a method known to those skilled in the art. That is, it can be obtained by reacting a heterocyclic ring-containing compound which is a ligand with a complex precursor containing a transition metal. As a method for synthesizing a ligand, a method known to those skilled in the art can be used. As a specific example, when the structure of the heterocycle is an oxazolyl group, a method of forming an oxazole ring using 2-aminobenzonitrile as a raw material can be mentioned. Specific synthetic examples are described in detail as examples of ligand synthesis in the examples. The synthetic route of the metal complex obtained by reacting the complex precursor with the ligand can be arbitrarily determined from 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 or divalent nickel or palladium compounds or complexes, particularly metal halides such as iron chloride, nickel chloride, palladium chloride; iron acetate, palladium acetate and the like. Acetate: A complex having ligands such as carbonyl, triphenylphosphine, acetylacetone, ^η4 -cyclooctadien, acetonitrile, pyridine and the like.

(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 0.7 to 1 mol of the heterocyclic ring-containing compound which is a ligand. It is in the range of 1.5 mol. The complex synthesis reaction may be carried out in a reactor used for copolymerization with α-olefin, or may be carried out in a container different 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 isolation.

<Second component>
In a further aspect, the catalyst composition of the present invention has the component (A) as the component (B) in addition to the transition metal complex represented by any of the general formulas (1) to (3) as the component (A). ) To form an ion pair or an ion-exchange layered silicate.

(1) A compound that reacts with the component (A) to form an ion pair As a compound that reacts with the component (A) to form an ion pair, which is one of the components (B), an organoaluminum oxy compound can be mentioned. .. The organoaluminum oxy compound has an Al—O—Al bond in the molecule, and the number of the bonds is usually in the range of 1 to 100, preferably 1 to 50. Such organoaluminum oxy compounds are usually products obtained by reacting organoaluminum compounds with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or It is preferable to use aromatic hydrocarbons.

As the organoaluminum compound used for preparing the organoaluminum oxy 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, an alkenyl group, an aryl group, an aralkyl group, etc., and X ₃ represents a hydrogen atom or a halogen atom. Indicated, t indicates an integer of 1 ≦ t ≦ 3.)
The alkyl group of trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and the like, but a methyl group. , Isobutyl group is preferable, and methyl group is particularly preferable. The above-mentioned organoaluminum compounds can also be used by mixing two or more kinds.

The reaction ratio (water / Al molar ratio) of water to the organoaluminum compound 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 −20 to 20 ° C. The reaction time is usually selected in 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 water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of producing water in the reaction system can be used. Of the above-mentioned organoaluminum oxy compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and in particular, methylaluminoxane (including those substantially composed of methylaluminoxane (MAO)). Is suitable as an organoaluminum oxy compound. Solid drymethylaluminoxane (DMAO) obtained by distilling off the MAO solution is also suitable.
Of course, as the organoaluminum oxy compound, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination, and a solution obtained by dissolving or dispersing the above-mentioned organoaluminum oxy compound in the above-mentioned inert hydrocarbon solvent. May be used.

Further, as another specific example of the component (B), a borane compound and a borate compound can be mentioned. More specifically, the above borane compounds are represented by triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tris (o-fluorophenyl) borane, and tris (o-fluorophenyl) borane. 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 (perfluoroanthril) borane and tris (perfluorobinaphthyl) borane.

Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) borane are more preferred, and even more preferably tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris ( Perfluoronaphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as preferred compounds.

Further, specifically expressing 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, and phosphonium.
Examples of ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tri (t-butyl) ammonium and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium. Can be exemplified. Examples of the anilinium include N, N-dialkylaniliniums such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-dimethyl-2,4,6-pentamethylanilinium. ..
Further, examples of phosphonium include triarylphosphonium such as triphenylphosphine, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

Further, 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 linked to each other by a bridging group. Also, as the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, and a halogen such as fluorine, chlorine, bromine and iodine are preferable. Further, X4 and X5 are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, and a substituted hydrocarbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms. Is.

Specific examples of the compound represented by the above general formula include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, and tributylammonium tetra (3,5-ditrifluoromethyl). Phenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethyl) Phenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluorophenyl) borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra ( Pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) Borate, Triphenylphosphonium Tetra (Perfluoronaphthyl) Borate, trimethylammonium Tetra (2,6-ditrifluoromethylphenyl) Borate, Triethylammonium Tetra (Pentafluorophenyl) Borate, Triethylammonium Tetra (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 can be exemplified.

Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro). Naftyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

The 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, a methyl cation, an ethyl cation, a propyl cation, an isopropyl cation, a butyl cation, an isobutyl cation, a t-butyl cation, a pentyl cation, a tropinium cation, a benzyl cation, a trityl cation, a sodium cation, and a proton. And so on. Further, 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, and the like. Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluorophenyl) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) borate, tropiniumtetra (p- Trill) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m-fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (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-F2 _- Ph) _{4, NaB (C6F3) 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 , 5- (CF ₃ ) _{2 -} Ph) 4.2 diethyl ether, HB (C ₁₀ H ₇ ) _4.2 diethyl ether can be exemplified. ..

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, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (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, HB (C ₁₀ H ₇ ) _4.2 diethyl ether is preferred.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluorofluoro) 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- (2, 6-) CF ₃ ) ₂ -Ph) 4.2 diethyl ether, HB (3,5- (CF ₃ ) _{2 -} Ph) 4.2 diethyl ether, HB ₍ C _{10H 7} ) _4.2 diethyl ether can be mentioned.

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

(2) Ion-exchangeable layered silicate Further, as a specific example of the component (B), an ion-exchangeable layered silicate (hereinafter, may be simply abbreviated as "silicate") can be mentioned. The ion-exchangeable layered silicate is a silicate compound having a crystal structure in which planes composed of ionic bonds and the like are stacked in parallel by a bonding force, and the contained ions can be exchanged. Various known silicates are known, and specifically, they are described in "Clay Minerals" by Haruo Shiramizu, Asakura Shoten (1995).
In the present invention, those preferably used as the ion-exchangeable layered silicate of the component (B) belong to the smectite group, and specifically, montmorillonite, saponite, byderite, nontronite, saponite, hectorite, and stephensite. And so on. Of these, montmorillonite is preferable from the viewpoint of increasing the polymerization activity and molecular weight of the copolymer portion.

Since most silicates are naturally produced mainly as the main component of clay minerals, they often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates, and are used in the present invention. The smectite silicates used may contain impurities.
The silicate may be acid-treated and / or salt-treated. In the treatment, the corresponding acid and base may be mixed to generate a salt in the reaction system for the treatment.

As the component (B), a mixture of the above-mentioned organoaluminum oxy compound, a borane compound, a borate compound, and an ion-exchangeable layered silicate can also be used. Further, each may be used alone, or two or more kinds may be used.

<Third component>
Yet another aspect of the present invention contains an alkylaluminum compound as the component (C) in addition to the components (A) and (B). An example of the alkylaluminum compound used as the 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 a hydrogen, a halogen, an alkoxy group or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, and halogen or alkoxy such as diethylaluminum monochloride and diethylaluminum monomethoxyde. Alkyl aluminum can be mentioned.

Of these, triisobutylaluminum is preferred. Further, two or more kinds of the above-mentioned organoaluminum compounds may be used in combination. Further, the above aluminum compound may be modified with alcohol, phenol or the like before use. Examples of these denaturants include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, 2,6-di-t-butylphenol and the like, and preferred specific examples are 2,6. -Dimethylphenol, 2,6-di-t-butylphenol.

<Preparation method of catalyst composition>
In the method for preparing the catalyst composition for olefin polymerization according to the present invention, for example, a method of contacting the components (A) and, if necessary, (B) and (C) is adopted. The specific method such as the contact order 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) After contacting component (A) and component (C), component (B) Method of adding component (iii) After contacting component (B) and component (C), method of adding component (A) (iv) Contacting each component (A), (B), (C) at the same time. How to make it.
Further, different kinds of components may be used as a mixture in each component, or they may be contacted separately in a different order. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with an olefin or the time of polymerization of an olefin. Further, the components may be divided and brought into contact with each component, for example, after the component (B) and the component (C) are brought into contact with each other, a mixture of the component (A) and the component (C) is added.

The contacts of the above components (A), (B) and (C) are preferably carried out in an inert gas such as nitrogen in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact can be carried out at a temperature between −20 ° C. and the boiling point of the solvent, and is particularly preferably carried out at a temperature between room temperature and the boiling point of the solvent.

<Polymerization method>
(1) Monomer The above-mentioned olefin polymerization catalyst can be used for homopolymerization of α-olefins or copolymerization of two or more types of α-olefins. The α-olefins include those having 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1. -Examples include penten. More preferably, ethylene and propylene may be mentioned. The α-olefins can also be copolymerized with 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 a small amount of comonomer other than α-olefin. In this case, styrenes such as styrene, 4-methylstyrene and 4-dimethylaminostyrene, 1,4-butadiene, 1,5-hexadiene, etc. Examples of compounds having a polymerizable double bond of 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 octene. Can be done.

(2) Polymerization method The polymerization reaction can be carried out in the presence of a catalyst, preferably by slurry polymerization, bulk polymerization or vapor 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 alicyclics such as cyclohexane and methylcyclohexane are substantially cut off. Ethylene and the like are polymerized in the presence or absence of an inert hydrocarbon solvent selected from group hydrocarbons. In addition, bulk polymerization using a liquid monomer such as liquid ethylene or liquid propylene as a solvent is also one of the preferable modes.

The polymerization conditions are such that the temperature is 0 to 250 ° C., preferably 20 to 110 ° C., more preferably 60 to 100 ° C., and the pressure is normal pressure to 10 MPa, preferably normal pressure to 4 MPa, still more preferably 0.5 to 2 MPa. The polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

Even if a component for the purpose of removing water, a so-called scavenger, is added to the polymerization system, it can be carried out without any problem. Examples of the scavenger include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, the above-mentioned organoaluminum oxy compound, modified organoaluminum compound containing branched alkyl, diethyl zinc, and dibutyl zinc. Organoaluminium compounds such as, diethylmagnesium, dibutylmagnesium, organomagnesium compounds such as ethylbutylmagnesium, and greenia compounds such as ethylmagnesium chloride and butylmagnesium chloride are used.
Among these, triethylaluminum, triisobutylaluminum, ethylbutylmagnesium and tri-n-octylaluminum are preferable, and triethylaluminum and triisobutylaluminum are particularly preferable.

The catalyst composition of the present invention can be applied without hindrance to a multi-step polymerization method having two or more steps in which the polymerization conditions are different from each other.

Hereinafter, the present invention will be specifically described with reference to Examples, and the rationality and significance of the configuration of the present invention and the excellence over the prior art will be demonstrated.

<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) manufactured by the company, flow velocity: 1.0 mL / min, injection volume: 0.2 mL
(Sample preparation) A 1 mg / mL solution is prepared using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), and the sample is prepared at 140 ° C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the conversion from the retained capacity to the molecular weight was performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all brands 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 solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each was 0.5 mg / mL. For the calibration curve, a cubic equation obtained by approximating with the least squares method was used. The following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to the 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 DSC6200 differential scanning calorimetry device manufactured by Seiko Instruments, a sheet-shaped sample piece was packed in a 5 mg aluminum pan, and the temperature was once raised from room temperature to 200 ° C. at a heating rate of 100 ° C./min and held for 5 minutes. Later, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final temperature rise 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]
About 250 mg of a sample formed into a film having a thickness of about 100 μm was weighed into a sample tube having an outer diameter of 10 mm, and 1.84 mL of ortho-dichlorobenzene and 0.46 mL of deuterated bromobenzene were added. After replacing the upper part of the sample tube with nitrogen, the sample tube was covered, and the sample was heated and melted in a high temperature bath at 130 ° C. until the sample became uniform.
[ ¹³ C-NMR measurement]
Measurements were performed using a Bruker Biospin AVANCE III400 NMR measuring device equipped with a cryoprobe under the condition of NOE-free by proton decoupling with a gate. The flip angle of the excitation pulse was 90 °, the pulse interval was 16.3 seconds, the measurement temperature was 120 ° C., the number of integrations was 500 or more, and the spectrum observation width was 24,0.38.5 Hz. ¹³ The attribution of the C-NMR spectrum was performed with reference to various documents.

The synthetic pathway of the transition metal complex in the present invention is shown below. Unless otherwise specified in the following synthesis examples, the operation was carried out in an inert gas atmosphere, and the solvent used was dehydrated and deoxidized.

工程１：２－（２－シアノアニリノ）ベンゾニトリルの合成
２－アミノベンゾニトリル１．０ｇ（８．５mmol）のジメチルスルホキシド１０mL溶液に、カリウム－ｔ－ブトキサイド１．９ｇ（１６．９mmol）と２－フルオロベンゾニトリル１．０ｇ（８．５mmol）を加えた。その後、室温で１２時間撹拌した。得られた反応溶液を氷水に投入し、ジクロロメタンで抽出した。有機層を水で洗浄し硫酸マグネシウム上で乾燥させ、減圧下溶媒を留去した。２－（２－シアノアニリノ）ベンゾニトリル１．０ｇの粗精物を黄色固体として得た。 [Example 1]
(1-1) Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) phenyl) amide iron dichloride (complex A)

Step 1: Synthesis of 2- (2-cyanoanilino) benzonitrile To a solution of 1.0 g (8.5 mmol) of 2-aminobenzonitrile in 10 mL of dimethyl sulfoxide, 1.9 g (16.9 mmol) of potassium-t-butoxide and 2- 1.0 g (8.5 mmol) of fluorobenzonitrile was added. Then, the mixture was stirred at room temperature for 12 hours. The obtained reaction solution was put into ice water and extracted with dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. A crude product of 1.0 g of 2- (2-cyanoanilino) benzonitrile was obtained as a yellow solid.

Step 2: Synthesis of bis (2- (4-phenyl-4,5-dihydrooxazolyl) phenyl) amine In a solution of 9.5 g (43.3 mmol) of 2- (2-cyanoanilino) benzonitrile in 150 mL of chlorobenzene. 23.6 g of zinc chloride and 23.8 g (173.3 mmol) of 2-amino-2-phenylethanol were added. Then, the mixture was stirred at 130 ° C. for 72 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 on a silica gel column gave 8.4 g (yield 42%) of bis (2- (4-phenyl-4,5-dihydrooxazolyl) phenyl) amine as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ4.00 (t, 2H), δ4.48 (t, 2H), δ5.18 (t, 2H), δ6.94 (t, 2H), δ7.25 (m, 10H), δ7.35 (t, 2H), δ7.55 (d, 2H), δ7.90 (d, 2H), δ11.11 (s, 1H),

Step 3: Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) phenyl) amide iron dichloride (complex A) synthetic bis (2- (4-phenyl-4) , 5-Dihydrooxazolyl) Phenyl) amine 1 g (2.2 mmol), iron (II) chloride 0.28 g (2.2 mmol), 15 mL of tetrahydrofuran (THF) were mixed and heated to reflux for 2 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane and 1.3 g of black-green crystals of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) phenyl) amide iron dichloride (yield). Rate 99%) was obtained.

(1-2) Ethylene polymerization by complex A 20 mg of complex A is dissolved in 10 mL of toluene, 20 mL of MMAO-3A / hexane solution (Al = 5.9 wt%, manufactured by Toso Finechem) is added thereto, and the mixture is stirred for 5 minutes. A complex solution was prepared.
790 mL of toluene was introduced into a stirring 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 press-fitted therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 30 minutes, ethanol was press-fitted, and the polymerization was stopped.
The obtained slurry was put into hydrochloric acid / ethanol and filtered, washed with ethanol and dried to obtain 8.3 g of a polymer. The activity of the catalyst was 488,000 (g-PE / mol-Fe / h), and the melting point of the obtained polymer was 135.6 (° C.).
The polymerization results are shown in Table 1.

工程１：Ｎ－（２－ブロモ－４－メチルフェニル）－２－ブロモ－４－メチルアニリンの合成
Ｎ－（４－メチルフェニル）－４－メチルアニリン３０ｇ（１５２mmol）の酢酸２００mL溶液を０℃に冷却し、臭素４６．９ｇ（２９３mmol）を滴下した。反応液を２０℃で１時間撹拌した後に、亜硫酸ナトリウム水溶液中に加えた。ろ過した固体をＥｔＯＨで洗浄し、ジクロロメタンに溶解した。有機層を炭酸水素ナトリウム水溶液で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を減圧留去させることにより、Ｎ－（２－ブロモ－４－メチルフェニル）－２－ブロモ－４－メチルアニリンの粗精製物５１．０ｇを白色固体として得た。 [Example 2]
(2-1) Synthesis of (N, N, N) -bis (2- (4-i-propyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex B)

Step 1: Synthesis of N- (2-bromo-4-methylphenyl) -2-bromo-4-methylaniline A solution of 30 g (152 mmol) of N- (4-methylphenyl) -4-methylaniline in 200 mL of acetic acid at 0 ° C. 46.9 g (293 mmol) of bromine was added dropwise. The reaction mixture was stirred at 20 ° C. for 1 hour and then added to an aqueous sodium sulfite solution. The filtered solid was washed with EtOH and dissolved in dichloromethane. The organic layer was washed with aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. By distilling off the solvent under reduced pressure, 51.0 g of a crude product of N- (2-bromo-4-methylphenyl) -2-bromo-4-methylaniline was obtained as a white solid.

Step 2: Synthesis of 2- (2-cyano-4-methyl-anilino) -5-methyl-benzonitrile N- (2-bromo-4-methylphenyl) -2-bromo-4-methylaniline 51.0 g ( 38.6 g (430 mmol) of copper (I) cyanide was added to a 250 mL solution of N-methylpyrrolidone (144 mmol). Then, it was heated at 140 ° C. for 72 hours. The reaction solution was added to aqueous ammonia and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was purified by a silica gel column to obtain 18 g (yield 51%) of the desired 2- (2-cyano-4-methyl-anilino) -5-methyl-benzonitrile as a pale yellow solid.

Step 3: Synthesis of 2- (4-i-propyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2- (2-cyano-4-methyl-anilino) -5-methyl- To a 15 mL solution of chlorobenzene of 2 g (8.1 mmol) of benzonitrile, 3.34 g (32.4 mmol) of (2S) -2-amino-3-methylbutane-1-ol and 2.8 g (20.2 mmol) of zinc chloride are added. rice field. The reaction mixture was heated to reflux for 8 days. After cooling the reaction solution, it was added to ethylenediamine and extracted with dichloromethane. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to obtain bis (2- (4-i-propyl-4,5-dihydrooxazolyl) -4-methylphenyl). 1.3 g (yield 38%) of amine was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ0.91 (d, 6H), δ1.02 (d, 6H), δ1.79 (m, 2H), δ2.30 (s, 6H), δ4.02 (t, 2H), δ4.08 (m, 2H), δ4.33 (t, 2H), δ7.09 (d, 2H), δ7.27 (d, 2H), δ7.62 (s, 2H) , δ10.46 (s, 1H).

Step 4: Synthesis of (N, N, N) -bis (2- (4-i-propyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex B) Bis (2-) Mix 2.0 g (4.8 mmol) of (4-i-propyl-4,5-dihydrooxazolyl) phenyl) amine, 0.6 g (4.8 mmol) of iron (II) chloride, and 20 mL of tetrahydrofuran (THF). It was heated and refluxed for 2 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane (N, N, N) -bis (2- (4-i-propyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride black-green. 2.4 g of crystals (yield 92%) were obtained.

(2-2) Ethylene Polymerization by Complex B 218 mg of Complex B was dissolved in 10 mL of toluene to prepare a complex solution.
790 mL of toluene was introduced into a stirring autoclave having an internal volume of 3 L, and then 21 mL of a MAO / toluene solution (Al = 20 wt%, manufactured by Nippon Aluminum Alkyls, Inc.) 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 press-fitted therein with _N2 . Ethylene pressure of 2.5 MPa was maintained for 60 minutes, and ethanol was press-fitted to terminate the polymerization.
The obtained slurry was put into hydrochloric acid / ethanol and filtered, washed with ethanol and dried to obtain 40.0 g of a polymer. The activity of the catalyst is 95,000 (g-PE / mol-Fe / h), the obtained polymer has a molecular weight (Mw) = 217,000, a molecular weight distribution (Mw / Mn) = 2.03, and a melting point of 136.7. It was (° C). The number of Me branches determined by NMR was 0.1 or less (pieces / 1000C).
The polymerization results are shown in Table 1.

[Example 3]
(3-1) Ethylene polymerization by complex B (2)
18 mg of complex B was dissolved in 10 mL of toluene, 20 mL of MMAO-3A / hexane solution (Al = 5.9 wt%) was added thereto, and the mixture was stirred for 5 minutes to prepare a complex solution.
790 mL of toluene was introduced into a stirring 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 press-fitted therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 30 minutes, and ethanol was press-fitted to terminate the polymerization.
The obtained slurry was put into hydrochloric acid / ethanol, filtered, washed with ethanol, and dried to obtain 1.0 g of a polymer. The activity of the catalyst was 59,000 (g-PE / mol-Fe / h), and the melting point of the obtained polymer was 136.5 (° C.).
The polymerization results are shown in Table 1.

工程１：ビス（２－（４，４－ジメチル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミンの合成
２－（２－シアノ－４－メチル－アニリノ）－５－メチル－ベンゾニトリル３．７ｇ（１５mmol）のクロロベンゼン４０mL溶液に、２－アミノ－２－メチルプロパン－１－オール８．３ｇ（９３mmol）、塩化亜鉛２０．０ｇ（１４６mmol）を加えた。反応液を６０時間加熱還流した。反応液を冷却後、エチレンジアミンを加え、ジクロロメタンで抽出した。有機層を無水硫酸ナトリウムで乾燥し、溶媒を減圧留去後、シリカゲルカラムで精製してビス（２－（４，４－ジメチル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミン０．８７ｇ（収率１５％）を黄色固体として得た。
^１H-NMR(400MHz,CDCl₃):δ1.37(s,12H),δ2.29(s,6H),δ4.03(s,4H),δ7.08(d,2H), δ7.28(d,2H), δ7.63(s,2H), δ10.28(s,1H). [Example 4]
(4-1) Synthesis of (N, N, N) -bis (2- (4,4-dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex C)

Step 1: Synthesis of bis (2- (4,4-dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2- (2-cyano-4-methyl-anilino) -5-methyl- To a solution of 3.7 g (15 mmol) of benzonitrile in 40 mL of chlorobenzene was added 8.3 g (93 mmol) of 2-amino-2-methylpropane-1-ol and 20.0 g (146 mmol) of zinc chloride. The reaction mixture was heated to reflux for 60 hours. After cooling the reaction solution, ethylenediamine was added and the mixture was extracted with dichloromethane. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to purify the bis (2- (4,4-dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine. 0.87 g (yield 15%) was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ1.37 (s, 12H), δ2.29 (s, 6H), δ4.03 (s, 4H), δ7.08 (d, 2H), δ7.28 (d, 2H), δ7.63 (s, 2H), δ10.28 (s, 1H).

Step 2: Synthesis of (N, N, N) -bis (2- (4,4-dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex C) synthetic bis (2-) (4,4-Dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2.0 g (5.1 mmol), iron (II) chloride 0.65 g (5.1 mmol), tetrahydrofuran (THF) 20 mL was mixed and heated to reflux for 5 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane, and (N, N, N) -bis (2- (4,4-dimethyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride 2. 3 g (yield 87%) was obtained as black-green crystals.

(4-2) Ethylene polymerization by complex C 18 mg of complex C was dissolved in 10 mL of toluene, 20 mL of MMAO-3A / hexane solution (Al = 5.9 wt%) was added thereto, and the mixture was stirred for 5 minutes to prepare the complex solution. ..
790 mL of toluene was introduced into a stirring 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 press-fitted therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 30 minutes, and ethanol was press-fitted to terminate the polymerization.
The obtained slurry was put into hydrochloric acid / ethanol, filtered, washed with ethanol, and dried to obtain 0.24 g of a polymer. The activity of the catalyst was 16,000 (g-PE / mol-Fe / h), and the melting point of the obtained polymer was 135.7 (° C.).
The polymerization results are shown in Table 1.

工程１：ビス（２－（４－フェニル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミンの合成
２－（２－シアノ－４－メチル－アニリノ）－５－メチル－ベンゾニトリル２．０ｇ（８．１mmol）のクロロベンゼン３０mL溶液に、（２Ｒ）－２－アミノ－２－フェニル－エタン－１－オール４．４ｇ（３２mmol）、塩化亜鉛４．４ｇ（３２mmol）を加えた。反応液を１３０℃で４０時間加熱した。反応液を冷却後、エチレンジアミンに加え、ジクロロメタンで抽出した。有機層を無水硫酸ナトリウムで乾燥し、溶媒を減圧留去後、シリカゲルカラムで精製してビス（２－（４－フェニル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミン３．１ｇ（収率７８％）を黄色固体として得た。
^１H-NMR(400MHz,CDCl₃):δ2.33(s,6H), δ3.99(t,2H), δ4.48(s,6H), δ5.19(s,6H), δ7.24(m,12H), δ7.42(d,2H), δ7.71(s,2H), δ10.82(s,1H). [Example 5]
(5-1) Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex D)

Step 1: Synthesis of bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2- (2-cyano-4-methyl-anilino) -5-methyl-benzonitrile To a solution of 2.0 g (8.1 mmol) of chlorobenzene in 30 mL, 4.4 g (32 mmol) of (2R) -2-amino-2-phenyl-ethane-1-ol and 4.4 g (32 mmol) of zinc chloride were added. The reaction solution was heated at 130 ° C. for 40 hours. After cooling the reaction solution, it was added to ethylenediamine and extracted with dichloromethane. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to purify the bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine. 1 g (yield 78%) was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ2.33 (s, 6H), δ3.99 (t, 2H), δ4.48 (s, 6H), δ5.19 (s, 6H), δ7.24 (m, 12H), δ7.42 (d, 2H), δ7.71 (s, 2H), δ10.82 (s, 1H).

Step 2: Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex D) Bis (2- (4) -Phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2.0 g (4.1 mmol), iron (II) chloride 0.52 g (4.1 mmol), THF 20 mL are mixed and heated for 5 hours. It circulated. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride 2.1 g (yield). A rate of 83%) was obtained as black-green crystals.

(5-2) Propylene Polymerization by Complex D 123 mg of complex D was dissolved in 10 mL of toluene, 6.3 mL of MAO / toluene solution (Al = 20 wt%) was added thereto, and the mixture was stirred for 5 minutes to prepare a complex solution.
After replacing the inside of the stirring autoclave having an internal volume of 3 L with propylene, 750 g of propylene was introduced, and then 3.2 mL of the MAO / toluene solution was press-fitted with _N2 . The temperature was raised to 70 ° C., and the previously prepared complex solution was press-fitted with _N2 . The temperature was maintained for 30 minutes and ethanol was press-fitted to terminate the polymerization.
The obtained polymer was put into hydrochloric acid / ethanol, filtered, washed with ethanol, and dried to obtain 0.1 g of the polymer. The activity of the catalyst is 1,000 (g-PP / mol-Fe / h), the obtained polymer has a molecular weight (Mw) = 1,018,000, a molecular weight distribution (Mw / Mn) = 3.4, and a melting point of 157. It was 9.9 (° C.).
The polymerization results are shown in Table 2.

[Example 6]
(6-1) Propylene Polymerization by Complex A 200 mg of complex A was dissolved in 10 mL of toluene, 40 mL of MMAO-3A / hexane solution (Al = 5.9 wt%) was added thereto, and the mixture was stirred for 5 minutes to prepare a complex solution. ..
After replacing the inside of the stirring autoclave having an internal volume of 3 L with propylene, 750 g of propylene was introduced, and then 40 mL of MMAO-3A / hexane solution was press-fitted with _N2 . The temperature was raised to 70 ° C., and the previously prepared complex solution was press-fitted with _N2 . The temperature was maintained for 60 minutes and ethanol was press-fitted to terminate the polymerization.
The obtained polymer was put into hydrochloric acid / ethanol, filtered, washed with ethanol, and dried to obtain 0.1 g of the polymer. The activity of the catalyst was 300 (g-PP / mol-Fe / h), and the melting point of the obtained polymer was 157.4 (° C.).

工程１：ビス（２－（４－メチル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミンの合成
２－（２－シアノ－４－メチル－アニリノ）－５－メチル－ベンゾニトリル８．０ｇ（３２mmol）のクロロベンゼン１５０mL溶液に、（２Ｒ）－２－アミノ－プロパン－１－オール９．７ｇ（１２９mmol）、塩化亜鉛１７．６ｇ（１２９mmol）を加えた。反応液を１９２時間加熱還流した。反応液を冷却後、エチレンジアミンに加え、ジクロロメタンで抽出した。有機層を無水硫酸ナトリウムで乾燥し、溶媒を減圧留去後、シリカゲルカラムで精製してビス（２－（４－メチル－４，５－ジヒドロオキサゾリル）－４－メチルフェニル）アミン ５．０ｇ（収率４２％）を黄色固体として得た。
^１H-NMR(400MHz,CDCl₃):δ1.37(d,6H),δ2.29(s,6H),δ3.88(s,2H),δ4.42(m,4H),δ7．08(d,2H),δ7.33(d,2H),δ7．62(s,2H),δ10.52(s,1H). [Example 7]
(7-1) Synthesis of (N, N, N) -bis (2- (4-methyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex E)

Step 1: Synthesis of bis (2- (4-methyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine 2- (2-cyano-4-methyl-anilino) -5-methyl-benzonitrile To a solution of 8.0 g (32 mmol) of chlorobenzene in 150 mL, 9.7 g (129 mmol) of (2R) -2-amino-propane-1-ol and 17.6 g (129 mmol) of zinc chloride were added. The reaction was heated to reflux for 192 hours. After cooling the reaction solution, it was added to ethylenediamine and extracted with dichloromethane. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to purify the bis (2- (4-methyl-4,5-dihydrooxazolyl) -4-methylphenyl) amine. 0 g (yield 42%) was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): δ1.37 (d, 6H), δ2.29 (s, 6H), δ3.88 (s, 2H), δ4.42 (m, 4H), δ7.08 (d, 2H), δ7.33 (d, 2H), δ7.62 (s, 2H), δ10.52 (s, 1H).

Step 2: Synthesis of (N, N, N) -bis (2- (4-methyl-4,5-dihydrooxazolyl) -4-methylphenyl) amide iron dichloride (complex E) Bis (4-methyl- 2.0 g (5.5 mmol) of 4,5-dihydrooxazolyl-4-methylphenyl) amine, 0.70 g (5.5 mmol) of iron (II) chloride, and 35 mL of THF were mixed and heated under reflux for 5 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane (N, N, N) -bis (4-methyl-4,5-dihydrooxazolyl-4-methylphenyl) amide iron dichloride 2.5 g (yield 93%). Was obtained as a black-green crystal.

(7-2) Ethylene polymerization by complex E 17 mg of complex E is dissolved in 10 mL of toluene, 20 mL of MMAO-3A / hexane solution (Al = 5.9 wt%, manufactured by Toso Finechem) is added thereto, and the mixture is stirred for 5 minutes. A complex solution was prepared.
790 mL of toluene was introduced into a stirring 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 press-fitted therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 30 minutes, ethanol was press-fitted, and the polymerization was stopped. The obtained slurry was put into hydrochloric acid / ethanol, filtered, washed with ethanol, and dried to obtain 0.5 g of a polymer. The activity of the catalyst was 29,000 (g-PE / mol-Fe / h), and the melting point of the obtained polymer was 135.4 (° C.).
The polymerization results are shown in Table 1.

工程１：ビス（２，４－ジメチルフェニル）アミンの合成
２，４－ジメチルアニリン ４．０ｇ（３３mmol）、１－ブロモ－２，４－ジメチルベンゼン６．１ｇ（３３mmol）、ナトリウム－ｔ－ブトキサイド６３ｍｇ（６６０μmol）と（ビス（ジフェニルホスフィノ）フェロセン）ジクロロパラジウム５８０ｍｇ（７９０μmol）のトルエン１００mL溶液を１００℃で１２時間撹拌した。
その後、得られた反応溶液を減圧留去し、ジクロロメタンで再溶解した。有機層を水で洗浄し、硫酸ナトリウムで乾燥させ、減圧下溶媒を留去した。ビス（２，４－ジメチルフェニル）アミン７．４ｇの粗精物を濃茶色固体として得た。 [Example 8]
(8-1): Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amide iron dichloride (complex F)

Step 1: Synthesis of bis (2,4-dimethylphenyl) amine 2,4-dimethylaniline 4.0 g (33 mmol), 1-bromo-2,4-dimethylbenzene 6.1 g (33 mmol), sodium-t-butoxyside A 100 mL solution of 63 mg (660 μmol) and (bis (diphenylphosphino) ferrocene) dichloropalladium 580 mg (790 μmol) in toluene was stirred at 100 ° C. for 12 hours.
Then, the obtained reaction solution was distilled off under reduced pressure and redissolved in dichloromethane. The organic layer was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. A crude product of 7.4 g of bis (2,4-dimethylphenyl) amine was obtained as a dark brown solid.

Step 2: Synthesis of bis (2-bromo-4,6-dimethylphenyl) amine To a solution of 3.0 g (13 mmol) of bis (2,4-dimethylphenyl) amine in 25 mL of acetic acid, 25 of 4.36 g (27 mmol) of bromine. Dropped at ° C. Then, the reaction solution was stirred at 20 ° C. for 12 hours. The reaction solution was added to water and extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by a silica gel column to obtain 2.0 g (yield 39%) of bis (2-bromo-4,6-dimethylphenyl) amine as a yellow solid.

Step 3: Synthesis of 2- (2-cyano-4,6-dimethyl-anilino) -3,5-dimethyl-benzonitrile 2.0 g (5.2 mmol) of bis (2-bromo-4,6-dimethylphenyl) amine ), 1.4 g (16 mmol) of copper cyanide was added to a 30 mL solution of N-methylpyrrolidone. Then, the reaction solution was stirred at 140 ° C. for 12 hours. After filtering the reaction solution with cerite, the filtrate was added to aqueous ammonia, and after filtration, the filtered solid was dissolved in dichloromethane. The organic layer was washed with aqueous ammonia and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue is purified by a silica gel column to give 0.18 g (yield 13%) of 2- (2-cyano-4,6-dimethyl-anilino) -3,5-dimethyl-benzonitrile as a yellow solid. Obtained.

Step 4: Synthesis of bis (2- (4-methyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amine 2- (2-cyano-4,6-dimethyl-anilino) -3, To a solution of 5.0 g (18 mmol) of 5-dimethyl-benzonitrile in 100 mL of chlorobenzene, 10.0 g (73 mmol) of (2R) -2-amino-2-phenylethanol and 9.9 g (73 mmol) of zinc chloride were added. The reaction mixture was heated to reflux for 144 hours.
After cooling the reaction solution, it was added to ethylenediamine and extracted with dichloromethane. The organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is purified on a silica gel column to purify the bis (2- (4-methyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amine. 2.6 g (yield 28%) was obtained as a yellow solid.
¹ H-NMR (400MHz, CDCl ₃ ): Isomer A: δ1.90 (s, 6H), δ2.16 (s, 6H), δ3.63 (t, 2H), δ4.96 (t, 2H) , δ5.20 (t, 2H), δ7.15 (m, 14H), δ9.99 (s, 1H), Isomer B: δ1.94 (s, 6H), δ2.24 (s, 6H), δ3.96 (t, 2H), δ4.19 (t, 2H), δ5.04 (t, 2H), δ7.15 (m, 14H), δ9.93 (s, 1H).

Step 5: Synthesis of (N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amide iron dichloride (complex F) Bis (2-) Mix 1.0 g (1.9 mmol) of (4-methyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amine, 0.35 g (1.9 mmol) of iron (II) chloride, and 10 mL of THF. , Heated and refluxed for 7 hours. After cooling, the reaction solution was filtered through Celite, and the solvent was distilled off under reduced pressure. It was recrystallized from dichloromethane / hexane and N, N, N) -bis (2- (4-phenyl-4,5-dihydrooxazolyl) -4,6-dimethylphenyl) amide iron dichloride 0.87 g ( (Yield 70%) was obtained as black-green crystals.

(8-2) Ethylene polymerization by complex F 28 mg of complex E is dissolved in 10 mL of toluene, 20 mL of MMAO-3A / hexane solution (Al = 5.9 wt%, manufactured by Toso Finechem) is added thereto, and the mixture is stirred for 5 minutes. A complex solution was prepared.
790 mL of toluene was introduced into a stirring 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 press-fitted therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 30 minutes, ethanol was press-fitted, and the polymerization was stopped.
The obtained slurry was put into hydrochloric acid / ethanol and filtered, washed with ethanol and dried to obtain 4.8 g of a polymer. The activity of the catalyst was 279,000 (g-PE / mol-Fe / h), and the melting point of the obtained polymer was 136.7 (° C.).
The polymerization results are shown in Table 1.

As is clear from Table 1, the catalyst composition of the present invention is useful as a polymerization catalyst for polyethylene. In particular, the obtained polyethylene has a very high melting point and very few branches of methyl groups, has a high density, and has excellent mechanical properties.

As shown in Table 2, it has been clarified that the catalyst composition of the present invention acts as an effective catalytic system for other α-olefins such as propylene. That is, since the catalyst composition of the present invention is a catalyst capable of producing a polyolefin having excellent various properties, it is very useful in the field of manufacturing and application of polyolefins such as film molding.

Claims (5)

A catalyst composition for α-olefin polymerization, which comprises a transition metal complex represented by the following general formula (3).

[During the ceremony,
R ¹ , R ² , R ⁵ to R ⁸ , R ¹¹ , R ¹² , R ¹⁵ to R ¹⁸ , and R ^a to R ^d are each independently a hydrocarbon atom, a halogen atom, and a hydrocarbon having 1 to 30 carbon atoms. A group, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms. Indicates a substituent selected from the group consisting of
M indicates an iron atom ,
n is 1 or 2
X is a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including oxygen or nitrogen, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. A substituent selected from the group consisting of 10 acyl groups, 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. Is shown. ] A catalyst composition for α-olefin polymerization, which comprises the following components (A) and (B).
Component (A): Catalyst composition for α-olefin polymerization according to claim 1. Component (B): A compound or an ion-exchangeable layered silicate that reacts with the component (A) to form an ion pair. The catalyst composition for α-olefin polymerization according to claim 2 , wherein the component (B) is an aluminoxane or a boron compound. The catalyst composition for α-olefin polymerization according to claim 2 or 3 , further comprising a component (C): an alkylaluminum compound. A method for producing an α-olefin polymer, which comprises polymerizing an α-olefin using the catalyst composition for α-olefin polymerization according to any one of claims 1 to 4 .