JP2022152808A - Method for producing olefinic copolymer - Google Patents

Abstract

To provide a catalyst that can be used as a catalyst for olefinic polymerization, allows the production of polyethylene, and facilitates precise evaluation of purity and the like after the production, and a method for producing an olefinic polymer using the same.SOLUTION: A method for producing an olefinic polymer includes the step of polymerizing an olefinic compound by using, as a polymerization catalyst component, a catalyst including a low-spin complex having metal atoms of group 8 or 9 in the periodic table.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a novel catalyst composition containing a complex having a specific structure. More specifically, the present invention relates to a catalyst composition containing a transition metal complex in a low spin state as an essential component, and an olefinic copolymer produced therefrom. It relates to the manufacturing method of

Among resin materials, olefin polymers are excellent in various properties such as physical properties and moldability, are highly economical and adaptable to environmental problems, and are very widely used 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 also many

In recent years, as a method for producing an olefin polymer having a polar group, a method employing a polar monomer in the polymerization stage has attracted attention. For this purpose, so-called post-metallocene, late transition metal complex catalysts have been developed and physical properties of olefin polymers have been controlled using them. As post-metallocene catalysts for olefin polymerization, paramagnetic iron complex catalysts such as tridentate iron complexes having a diiminopyridine skeleton and bisaryliminopyridine iron are used, and the results of ethylene polymerization with these catalysts are known. (Patent Documents 1 to 3, Non-Patent Document 1). In addition, ethylene polymerization using paramagnetic iron complexes and cobalt complexes is known (Patent Documents 4 and 5, Non-Patent Documents 2 and 3). Also, as a catalyst design using ligands, a Group 10 complex called a SHOP catalyst is known (Patent Document 6).

Japanese Patent Publication No. 2006-501067 Japanese Patent No. 4108141 Japanese translation of PCT publication No. 2002-513823 JP 2018-172644 A JP 2020-056021 A Japanese Patent No. 5292059

Campora et al. Organometallics, 2005, 24, 4878-4881 Britovsek et al. Chem. Commun. 1998, 849. Britovsek et al. J. Am. Chem. Soc. 1999, 121, 8728.

Ethylene polymerization using a metal complex catalyst has been reported as described above. important for evaluation. However, regarding 8-9 group complex catalysts, in Patent Documents 1, 2, 3, 4, and 5 and Non-Patent Documents 1, 2, and 3, transition metal complexes in a high spin state are used, and NMR-like It is not possible to identify the catalyst and evaluate its purity by the commonly used methods. Accurately evaluating the purity of the catalyst not only leads to correct evaluation of its function as a polymerization catalyst, but also is a problem related to the reproducibility of olefin polymerization. Thus, there is a demand for the development of a catalyst that can be used as an olefin-based polymerization catalyst, that enables the production of polyethylene, and that can be easily and accurately evaluated for purity and the like after production.

An object of the present invention is to create a catalyst composition that can be easily evaluated for purity and the like and functions effectively as an olefin polymerization catalyst. As a result of intensive studies aimed at solving the above problems, the present inventors have found that a composition containing a specific iron complex functions as a component of a polymerization catalyst that meets the above objects, and have completed the present invention. came to create.

In a first aspect of the present invention, an olefin-based polymer comprising a step of polymerizing an olefin monomer using a catalyst containing a complex having a metal atom of group 8 or 9 of the periodic table in a low spin state as a polymerization catalyst component. A manufacturing method is provided.

In a second aspect of the present invention, the process for producing an olefin polymer according to the first aspect, wherein the complex has a tridentate or tetradentate ligand having a phosphorus atom as a coordination site. is provided.

［一般式（１）中、
Ｍは、酸化数が＋２の鉄、酸化数が＋２のルテニウム、酸化数が＋１のコバルト又は酸化数が＋１のロジウムであり、
ｎは、０又は１の整数を表し、
Ｒ^１ａ、Ｒ^１ｂ、Ｒ^１ｃ及びＲ^１ｄは、それぞれ独立して、炭素数３～１２の炭化水素基を表し、
Ｒ^２ａ及びＲ^２ｂは、それぞれ独立して、水素原子又は炭素数１～３の炭化水素を表し、
Ｒ^３ａ、Ｒ^３ｂ、Ｒ^３ｃ、Ｒ^３ｄ、Ｒ^３ｅ、Ｒ^３ｆ、Ｒ^３ｇ及びＲ^３ｈは、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～３０の炭化水素基、炭素数１～４のアルコキシ基、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表し、
Ｒ^４ａ及びＲ^４ｂは、それぞれ独立して、水素原子又は炭素数１～４の炭化水素基を表すか、あるいはＲ^４ａ及びＲ^４ｂは、互いに連結して環を形成し、
Ｌは、各登場においてそれぞれ独立して、中性の単座配位子、又はアニオン性の単座配位子から選択される金属の補助配位子を表し、
Ｘは、存在しないか、又は、－１価若しくは２価のカウンターアニオン種である。］ A third aspect of the present invention provides the method for producing an olefin polymer according to the first or second aspect, wherein the complex is represented by the following general formula (1).

[In general formula (1),
M is iron with an oxidation number of +2, ruthenium with an oxidation number of +2, cobalt with an oxidation number of +1 or rhodium with an oxidation number of +1;
n represents an integer of 0 or 1,
R ^1a , R ^1b , R ^1c and R ^1d each independently represent a hydrocarbon group having 3 to 12 carbon atoms,
R ^2a and R ^2b each independently represent a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms,
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 to 4 alkoxy 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 hydrocarbon group having 1 to 30 carbon atoms substituted with represents a substituent selected from the group consisting of silyl groups,
R ^4a and R ^4b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, or R ^4a and R ^4b are linked to each other to form a ring,
L independently at each occurrence represents a metal ancillary ligand selected from neutral monodentate ligands or anionic monodentate ligands;
X is absent or is a -1 or -2 counter anion species. ]

In a fourth aspect of the present invention, M in the formula (1) is iron with an oxidation number of +2 or ruthenium with an oxidation number of +2. A manufacturing method is provided.

A fifth aspect of the present invention is the method for producing an olefin polymer according to any one of the first to fourth aspects, wherein the obtained olefin polymer has a weight average molecular weight of 100,000 or more and 10,000,000. A method for producing an olefinic polymer is provided, characterized by the following.

The catalyst composition of the present invention provides a novel olefinic polymerization catalyst. Since the catalyst can be measured by NMR, the purity of the metal complex can be specified, and a catalyst containing a highly pure metal complex can be used as a polymerization catalyst component. INDUSTRIAL APPLICABILITY The metal complex-based polyolefin polymerization catalyst of the present invention and the olefin polymerization method using the same are very useful from an industrial point of view.

3 is a ³¹ P-NMR chart of Fe(II) complex A of Example 1. FIG. 1 is a ¹ H-NMR chart of Fe(II) complex A of Example 1. FIG. ³¹ P-NMR chart of Fe(II) complex B of Example 2. FIG. 1 is a ¹ H-NMR chart of Fe(II) complex B of Example 2. FIG.

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

<Transition metal complex>
The polymerization catalyst component used in the method of the present invention contains a transition metal complex containing a metal atom of group VIII or IX of the periodic table in a low spin state as a polymerization catalyst component. The type of transition metal complex is not particularly limited as long as it is a group 8 or 9 metal complex and can be identified by NMR measurement. NMR measurements are preferably sensitive and observe nuclides that result in simple peaks. Specific NMR measurement methods include ¹ H-NMR and ³¹ P-NMR, and NMR that measures these nuclides is preferable because the peaks appear clearly and the measurement environment is often ready. . ³¹ P-NMR is particularly preferred when the ligand contains a phosphorus atom. In ³¹ P-NMR, the position of the signal changes depending on the atoms and functional groups surrounding the phosphorus atom. to two. Moreover, since a characteristic peak is observed by coordinating to a metal atom, it is preferable that the phosphorus atom is in the coordination site and is coordinately bonded to the metal atom. More preferably, the transition metal complex has a tridentate or tetradentate ligand having at least one or more phosphorus atoms in its coordination position.

When the ligand is a tridentate ligand, a ligand having a structure (hereinafter referred to as PNP) having a phosphorus atom, a nitrogen atom, and a phosphorus atom in a clockwise direction, such as the following general formula (2), or A ligand having a structure having a phosphorus atom, a nitrogen atom, and a nitrogen atom clockwise (hereinafter referred to as PNN), such as the following general formula (3), may be mentioned. When the ligand is a tetradentate ligand, a tetradentate coordination of a structure (hereinafter referred to as PNNP) having a phosphorus atom, a nitrogen atom, a nitrogen atom, and a phosphorus atom clockwise as shown in the general formula (1) Children are a typical example. Such a ligand generally tends to form a regular octahedral complex structure, and as a result, the Group 8 or 9 metal complex is believed to easily assume a paramagnetic and low-spin state. In general formulas (2) and (3), R ^1a , R ^1b , R ^2a , R ^3a , R ^3b , R ^3c , R ^3d , R ^4a , R ^4b and n are As defined, R ⁵ has the same definition as R ^1a above.

A sample in NMR measurement is desirably a solution in terms of sensitivity. Therefore, the transition metal complex used in the method of the present invention is preferably soluble in an organic solvent. In particular, it is preferably dissolved in heavy benzene, heavy toluene, heavy acetone, heavy acetonitrile, methylene dichloride, or heavy chloroform. The solubility of the transition metal complex is preferably at least the level (1 g/L) required for ³¹ P-NMR measurement.

The transition metal complex used in the method of the present invention comprises a low spin state Group VIII or IX metal atom. Group 8 or 9 transition metals have 6 or 7 electrons in 5 d orbitals, and the number of unpaired electrons varies depending on the mode of orbital filling. By "low spin" is meant a state in which the number of unpaired electrons is zero. Examples of metal species that can be employed include +2 iron, ruthenium or osmium, +1 cobalt, rhodium or iridium.

［一般式（１）中、
Ｍは、酸化数が＋２の鉄、酸化数が＋２のルテニウム、酸化数が＋１のコバルト又は酸化数が＋１のロジウムであり、
ｎは、０又は１の整数を表し、
Ｒ^１ａ、Ｒ^１ｂ、Ｒ^１ｃ及びＲ^１ｄは、それぞれ独立して、炭素数３～１２の炭化水素基を表し、
Ｒ^２ａ及びＲ^２ｂは、それぞれ独立して、水素原子又は炭素数１～３の炭化水素を表し、
Ｒ^３ａ、Ｒ^３ｂ、Ｒ^３ｃ、Ｒ^３ｄ、Ｒ^３ｅ、Ｒ^３ｆ、Ｒ^３ｇ及びＲ^３ｈは、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～３０の炭化水素基、炭素数１～４のアルコキシ基、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表し、
Ｒ^４ａ及びＲ^４ｂは、それぞれ独立して、水素原子又は炭素数１～４の炭化水素基を表すか、又はＲ^４ａ及びＲ^４ｂは、互いに連結して環を形成し、
Ｌは、各登場においてそれぞれ独立して、中性の単座配位子、又はアニオン性の単座配位子から選択される金属の補助配位子を表し、
Ｘは、存在しないか、又は、－１価若しくは２価のカウンターアニオン種である。］ Specific examples of transition metal complexes used in the method of the present invention include transition metal complexes represented by the following general formula (1).

[In general formula (1),
M is iron with an oxidation number of +2, ruthenium with an oxidation number of +2, cobalt with an oxidation number of +1 or rhodium with an oxidation number of +1;
n represents an integer of 0 or 1,
R ^1a , R ^1b , R ^1c and R ^1d each independently represent a hydrocarbon group having 3 to 12 carbon atoms,
R ^2a and R ^2b each independently represent a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms,
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 to 4 alkoxy 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 hydrocarbon group having 1 to 30 carbon atoms substituted with represents a substituent selected from the group consisting of silyl groups,
R ^4a and R ^4b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, or R ^4a and R ^4b are linked to each other to form a ring,
L independently at each occurrence represents a metal ancillary ligand selected from neutral monodentate ligands or anionic monodentate ligands;
X is absent or is a -1 or -2 counter anion species. ]

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

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, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, t-butyl, 1-pentyl, 1-hexyl and 1-heptyl. 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 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, menthyl group, neomenthyl group, neopentyl group, 5-decyl group and the like. Among these, preferred substituents are isopropyl group, isobutyl group and cyclohexyl group.

Alkenyl groups include vinyl, allyl, butenyl, cinnamyl and styryl groups.

The aryl group includes 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 and substituted phenyl groups, and specific examples of preferred substituents for substituted phenyl groups are methyl, ethyl and phenyl groups, and particularly preferably, is a methyl group.

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

The “alkoxy group” means a hydrocarbon group having an oxygen atom bonded to its terminal, wherein the oxygen is not bonded to an aromatic ring. An alkoxy group having 1 to 4 carbon atoms is preferred, and preferred specific examples include methoxy, ethoxy, isopropoxy, 1-propoxy, 1-butoxy and t-butoxy. Among these, more preferred substituents are methoxy group, ethoxy group and isopropoxy group, and particularly preferred is methoxy group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group preferably includes a structure in which the aforementioned hydrocarbon group having 1 to 30 carbon atoms is substituted with an alkoxy group. Specific preferred examples include a methoxymethyl group, a methoxyethyl group, and the like.

The term "silyl group" means a silicon-terminated substituent, 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. Examples are trimethylsilyl, dimethylphenylsilyl, diphenylmethylphenylsilyl, triphenylsilyl groups. Among these, more preferred substituents are trimethylsilyl group and dimethylphenylsilyl group, and particularly preferred is trimethylsilyl group.

M in the general formula (1) is a group 8 or 9 transition metal, especially from iron with an oxidation number of +2, ruthenium with an oxidation number of +2, cobalt with an oxidation number of +1 or rhodium with an oxidation number of +1. selected from the group consisting of Preferably, it is iron with an oxidation number of +2 or cobalt with an oxidation number of +1.

In the portion corresponding to the tetradentate ligand in general formula (1), n represents an integer of 0 or 1. When the value of n is 0, the carbon to which ^R4a is bonded and the carbon to which ^R4b is bonded are directly bonded. The value of n is preferably 0 because there are many kinds of raw materials for ligand synthesis.

R ^1a , R ^1b , R ^1c and R ^1d each independently represent a hydrocarbon group having 3 to 12 carbon atoms. R ^1a , R ^1b , R ^1c and R ^1d may be the same or different, but the availability of the raw material compound, the ease of ligand synthesis, and the steric From the viewpoint of controlling the physical environment, each group is preferably the same group. Examples of R ^1a to R ^1d include alkyl groups having 3 to 12 carbon atoms, especially isopropyl group and t-butyl group; cycloalkyl groups having 3 to 12 carbon atoms, especially cyclohexyl groups; and aryl groups having 6 to 12 carbon atoms. , in particular phenyl, toluyl, naphthyl and the like. Among these, alkylaryl groups such as phenyl group, toluyl group and naphthyl group are preferred, alkylaryl groups having no substituents at the 2 and 6-positions are more preferred, and phenyl group is preferred. Especially preferred. R ^1a , R ^1b , R ^1c and R ^1b preferably have appropriate sizes from the viewpoint of polymer molecular weight, polymerization activity and ease of synthesis.

R ^2a and R ^2b each independently represent a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms. The radicals R ^2a and R ^2b make it possible to control the electronic state of the metal M via the nitrogen atom and can be selected without restriction within the above ranges. A hydrogen atom is desirably selected from the viewpoint of increasing the yield of ligand synthesis.

R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a halogen atom a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group substituted with a hydrocarbon having 1 to 4 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and a hydrocarbon group having 1 to 30 carbon atoms It represents a substituent selected from the group consisting of silyl groups substituted with hydrocarbon groups. A hydrogen atom is preferable from the viewpoint of suppressing the steric bulkiness of the ligand as a whole. In particular, it is preferable that R ^3d and R ^3e are hydrogen atoms, because the steric state can be easily controlled by R ^1a to R ^1d . Moreover, it is preferable that R ^3a and R ^3e are hydrogen atoms, since ligand synthesis can be facilitated. When any of R ^3a to R ^3h has a group other than a hydrogen atom as a substituent, R ^3b and R ^3g preferably have a substituent from the standpoint of availability. Further, R ^3b , R ^3c , R ^3g and R ^3h are desirably a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom from the viewpoint of improving the solubility of the entire complex.

R ^4a and R ^4b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, or R ^4a and R ^4b may be linked together to form a ring. It can be selected without being limited within the above range depending on the synthetic raw material of the ligand. When R ^4a and R ^4b are linked together to form a ring, the ring structure may be an alicyclic, heterocyclic or aromatic ring. The number of ring members is preferably 5-8. In terms of synthesis cost, raw material procurement is advantageous when both R ^4a and R ^4b are hydrogen atoms or both are methyl groups.

L at each occurrence independently represents a metal ancillary ligand selected from neutral monodentate ligands or anionic monodentate ligands. A neutral monodentate ligand is, for example, a ligand that is electrically neutral and can form a coordinate bond by coordinating an unpaired electron to the central metal M. is a molecule having a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, a selenium atom, etc. Yet another example is a molecule such as ethylene that forms a π-dative bond by donating a π-electron. Neutral monodentate ligands that can be used as L include those known as neutral ligands for metal complexes, such as acetonitrile, isonitrile, carbon monoxide, ethylene, and tetrahydrofuran. Anionic monodentate ligands are, by way of example, ligands that formally can take the form of donating an even number of electrons to a metal atom, halogens, alkyl groups, aryl groups, alkoxides, amides. , a silyl group, and the like. Among these, neutral monodentate ligands with weak coordinating power are desirable because they tend to lead to high catalytic activity. Acetonitrile and ethylene are particularly preferred.

X is absent or is a -1 or -2 counter anion species. when M is +2 valent iron or ruthenium and both L are anionic monodentate ligands, and when M is +1 valent cobalt or rhodium and one of L is an anionic monodentate ligand then X does not exist. When X is present, its valence and what kind of anion species it is are selected according to the valence of the complex moiety formed around the metal M. The -monovalent anion species include halide ions, NO ₃ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ , and the like. The -divalent anion species include SO ₄ ^2- , SO ₃ ^2- , CO ₃ ^2- , FeCl ₄ ^2- and the like. Among them, SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ , etc., which are weakly coordinative to metals, are desirable from the viewpoint of catalytic activity.

Preferred specific examples of the transition metal complex having a tetradentate ligand represented by formula (1) 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 Synthetic Route Synthesis of the transition metal complex used in the method of the present invention can be carried out using methods known to those skilled in the art. That is, it can be obtained by reacting a compound that is a ligand with a complex precursor containing a transition metal. Conditions such as reaction temperature, reaction solvent, atmosphere, and time can be appropriately selected from known conditions according to the ligand and complex precursor used. Since many of them are unstable with respect to water and oxygen, it is preferable to carry out in a dehydrated/deoxidized atmosphere. Methods known to those skilled in the art can also be used to synthesize ligands. As a specific example, when the structure of the ligand includes phosphine and imine, a method of condensing an aldehyde having a phosphine as a raw material with an amine compound may be used. The synthesis route of the metal complex obtained by reacting the complex precursor and the ligand can be arbitrarily determined from the structure of the target compound.

(2) Complex precursor The complex precursor is a Group 8-9 transition metal compound. Preferred specific examples are divalent iron or ruthenium, monovalent or trivalent cobalt or rhodium compounds or complexes, particularly metal halides such as iron chloride, cobalt chloride and ruthenium chloride; Acetate; a complex having ligands such as carbonyl, triphenylphosphine, acetylacetone, η4-cyclooctadiene, acetonitrile and pyridine.

(3) Reaction with Complex Precursor The amount of the complex precursor used in the preparation of the transition metal complex used in the method of the present invention is generally 0.5 mol to 3 mol, preferably 0.5 mol to 3 mol, per 1 mol of the ligand. It ranges from 7 mol to 1.5 mol. The reaction between the ligand and the complex (complex synthesis reaction) may be carried out in the reactor used for copolymerization with the α-olefin, or may be carried out in a vessel separate from the reactor. After the complex synthesis reaction, the complex may be isolated and extracted before use as a catalyst, or may be used as a catalyst without isolation. In any case, it is desirable to determine the purity of the complex by NMR measurement.

<Second component>
In a further aspect, the olefin-based polymerization catalyst of the present invention has a transition metal complex represented by the general formula (1) or a ligand represented by the general formula (2) or (3) as the component (A). In addition to the transition metal complex, it may be a composition containing, as component (B), a compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair.

(1) Compound that forms an ion pair by reacting with the component (A) Examples of the compound that forms an ion pair by reacting with the component (A), which is one of the components (B), include organoaluminum oxy compounds. . The organoaluminumoxy compound has an Al--O--Al bond in the molecule, and the number of such bonds is usually in the range of 1-100, preferably 1-50. Such an organoaluminumoxy compound is usually a product obtained by reacting an organoaluminum compound with water.
The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon (solvent). As inert hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use aromatic hydrocarbons.

Any compound represented by the following general formula can be used as the organoaluminum compound used for preparing the organoaluminumoxy compound, but trialkylaluminum is preferably used.
(R ₁ ) _t Al(X ₃ ) _(3−t)
(In the above formula, R ₁ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, and X ₃ represents a hydrogen atom or a halogen atom. and t is an integer of 1≤t≤3.)
The alkyl group of trialkylaluminum may 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 and the like. , an isobutyl group are preferred, and a methyl group is particularly preferred. Two or more of the organoaluminum compounds may 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 preferably 0.5/1 to 1/1, and the reaction temperature is , usually in the range of -70°C to 100°C, preferably -20°C 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, etc., and components capable of generating water in the reaction system can be used. Among the organoaluminumoxy compounds described above, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, particularly methylaluminoxane (including those substantially composed of methylaluminoxane (MAO)). is suitable as the organoaluminum oxy compound. Solid dry methylaluminoxane (DMAO) obtained by evaporating an MAO solution is also suitable.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can also be used in combination. You may use the one with

Further, other specific examples of component (B) include borane compounds and borate compounds. More specifically, the borane compounds are 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 (perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane, and the like.

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, and tris(perfluorobinaphthyl)borane are more preferred, and more preferably tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris( Preferred compounds include perfluoronaphthyl)borane and tris(perfluorobiphenyl)borane.

Further, when specifically representing the borate compound, a 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 Bronsted acids 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 anilinium include N,N-dialkylanilinium such as N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-dimethyl-2,4,6-pentamethylanilinium. .
Phosphoniums further include triarylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium, and trialkylphosphoniums.

Also, 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. The substituents of the substituted aromatic hydrocarbon group are preferably alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group, and halogens 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 by 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, 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, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(2,6-difluorophenyl)borate, dimethylaniliniumtetra(perfluoronaphthyl)borate, triphenylphosphonium tetra( pentafluorophenyl)borate, triphenylphosphonium tetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(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.

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

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 carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, t-butyl cation, pentyl cation, tropynium cation, benzyl cation, trityl cation, sodium cation, proton etc. Also, 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, tropinium tetraphenylborate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p- tolyl)borate, tropiniumtetra(m-tolyl)borate, tropiniumtetra(o-fluorophenyl)borate, tropiniumtetra(p-fluorophenyl)borate, tropiniumtetra(m-fluorophenyl)borate, tropiniumtetra (3,5-difluorophenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropiniumtetra(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(mF-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 , 5- ₍ CF ₃ ) ₂ -Ph) 4.2 diethyl ether and 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, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB( _C6F3 ) ₄ , NaB(2,6-( _CF3 ) ₂ -Ph) ₄ , NaB(3,5-( _CF3 ) _{2 -} Ph) ₄ , NaB _{( C10F7} ) 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-ditrifluoro 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-( 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 compounds exemplified above, the component (B) is preferably an aluminoxane or a boron compound.

(2) Ion-exchangeable phyllosilicate Furthermore, as a specific example of the component (B), an ion-exchanged phyllosilicate (hereinafter sometimes simply abbreviated as "silicate") can be mentioned. The ion-exchangeable layered silicate refers to a silicate compound that has a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other by bonding force, and in which the contained ions are exchangeable. Various known silicates are known, and specific examples are described in Haruo Shiramizu, Clay Mineralogy, Asakura Shoten (1995).
In the present invention, those preferably used as the ion-exchanged layered silicate of the component (B) belong to the smectite group, specifically montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, and stevensite. etc. can be mentioned. Among them, 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 a main component of clay minerals, they often contain contaminants (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. The smectite silicate used may contain impurities.
The silicate may be subjected to acid treatment and/or salt treatment. In the treatment, the corresponding acid and base may be mixed to form a salt in the reaction system.

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

<Third component>
Yet another aspect of the present invention contains an alkylaluminum compound as component (C) in addition to components (A) and (B). An example of the alkylaluminum compound used as component (C) is represented by the following general formula.
Al(R4) _{aX (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 3 or less.
Specific examples of the organoaluminum compounds represented by the general formula include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, and halogen- or alkoxy-containing compounds such as diethylaluminum monochloride and diethylaluminum monomethoxide. Alkyl aluminum is mentioned.

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

<Method for preparing catalyst composition>
In one aspect of the present invention, a method for preparing an olefin-based polymerization catalyst includes, for example, a method of contacting component (A) and, if necessary, (B) and (C). Although specific methods such as contact order are not particularly limited, the following methods can be exemplified.
(i) A method of adding component (C) after contacting component (A) with component (B) (ii) After contacting component (A) with component (C), component (B) (iii) A method of adding component (A) after contacting component (B) and component (C) (iv) Contacting each component (A), (B), (C) at the same time how to let
Furthermore, different components may be used as a mixture in each component, or may be brought into contact separately in different orders. This contact may be carried out not only during catalyst preparation but also during prepolymerization with olefins or during polymerization of olefins. Alternatively, the components may be divided and brought into contact with each component, such as by adding a mixture of components (A) and (C) after component (B) and component (C) are brought into contact.

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

<Polymerization method>
(1) Monomer The olefin polymerization catalyst containing the Group 8 or Group 9 complex described above can be used for homopolymerization of α-olefins or copolymerization of two or more α-olefins. α-Olefins include those having 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, specifically ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1 - Pentene and the like are exemplified. Ethylene and propylene are more preferred. Two or more types of α-olefins can be copolymerized. Copolymerization may be alternating copolymerization, random copolymerization, or block copolymerization. Of course, it is also possible to use small amounts of comonomers other than α-olefins. Dienes such as 1,4-hexadiene and 1,7-octadiene, cyclic compounds such as norbornene and cyclopentene, hexenol, hexenoic acid, methyl octenate, methyl acrylate, methyl methacrylate, methoxystyrene, vinyl acetate, etc. Compounds with polymerizable double bonds of oxygen compounds can be mentioned.

(2) Polymerization method The polymerization reaction can be carried out in the presence of the olefin-based polymerization 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 hydrocarbons such as cyclohexane and methylcyclohexane are used in a state in which oxygen and water are substantially cut off. Ethylene or the like is polymerized in the presence of an inert hydrocarbon solvent selected from group hydrocarbons. Bulk polymerization in which a liquid monomer such as liquid ethylene or liquid propylene is also used as a solvent is also a preferred embodiment.

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

A so-called scavenger may be added to the polymerization system without causing any trouble. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-octylaluminum, the aforementioned organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, diethyl zinc and dibutyl zinc. organozinc compounds such as diethylmagnesium, dibutylmagnesium and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride.
Among these, triethylaluminum, triisobutylaluminum, ethylbutylmagnesium and tri-n-octylaluminum are preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

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

In the following, the present invention will be specifically described by way of examples, demonstrating the rationality and significance of the configuration of the present invention and its superiority over the prior art.

<Evaluation method>

(1) NMR measurement of metal complex
[Sample preparation]
In a nitrogen-purged glove box, 20 mg of the complex sample, 0.7 ml of deuterated acetonitrile, and 5.0 mg of tris(orthotoluyl)phosphine as an arbitrary internal standard substance were placed in an NMR sample tube with an inner diameter of 5 mmφ, sealed, and then heated to room temperature. for 10 minutes, and the solution was uniformly dissolved and used for ³¹ P-NMR and ¹ H-NMR measurements.
[ ^31P -NMR measurement]
For NMR measurement, a Bruker Japan KK AV400 type NMR apparatus equipped with a 5 mmφ normal probe was used. The measurement conditions of ³¹ P-NMR were a sample temperature of 30° C., a pulse angle of 45°, a pulse interval of 2.76 seconds, and an accumulation number of 256 times. The chemical shift was obtained based on the external standard of the apparatus. The purity of the complex is obtained by obtaining the molar concentration of the complex from the peak area ratio with the internal standard substance, and converting it into the concentration of the complex in 20 mg of the sample. However, when there was only one peak derived from the target complex, the purity was judged to be 100%.
[ ¹ H-NMR measurement]
For NMR measurement, a Bruker Japan KK AV400 type NMR apparatus equipped with a 5 mmφ normal probe was used. The measurement conditions of ¹ H-NMR were a sample temperature of 30° C., a pulse angle of 45°, a pulse interval of 2.76 seconds, and an integration count of 16 times. Chemical shifts were determined based on the acetonitrile peak in deuterated acetonitrile.
(2) 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: ortho-dichlorobenzene (ODCB), column: Showa Denko Company AD806M/S (3), flow rate: 1.0 mL/min, injection volume: 0.2 mL
(Preparation of sample) A 1 mg/mL solution was prepared using ODCB (containing 0.5 mg/mL of BHT (2,6-di-t-butyl-4-methylphenol)), and It took about 1 hour to dissolve.
(Calculation of molecular weight) A standard polystyrene method was used, and the retention volume was converted into a molecular weight using a previously prepared standard polystyrene calibration curve. The standard polystyrenes used are all Tosoh brands F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500 and A1000. A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL of BHT) so that each concentration would be 0.5 mg/mL. A cubic equation obtained by approximation by the least-squares method was used for the calibration curve. The following numerical values were 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

The synthesis route of the transition metal complex in the present invention is shown below. For synthesis, reference was made to non-patent literature: Sui-Seng et al. Angew. Chem. Int. Ed. In the synthesis examples below, unless otherwise specified, the operations were carried out in an inert gas atmosphere, and dehydrated and deoxygenated solvents were used.

シュレンク管に（Ｓ，Ｓ）－Ｎ，Ｎ－ビス［２－（ジフェニルホスフィノ）ベンジリデン］シクロヘキサン－１，２－ジアミンを３００ｍｇ（０．４５５ｍｍｏｌ）量り取り、アセトニトリルを１０ｍL加えた。ここに、アセトニトリル２ｍLに溶解させた塩化鉄（２）１１５ｍｇ（０．９１ｍｍｏｌ）を室温で加え、１時間撹拌した。その後溶媒を２ｍL程度残して留去し、残留物をエーテル２０ｍLで洗浄した。洗浄後、溶媒を完全に留去してからクロロホルムを１５ｍL加え、不溶物をガラスフィルターで除去した。回収した溶液を完全に乾固し、クロロホルム５ｍLとヘキサン２０ｍLで再結晶することで２１１ｍｇの固体を得た。
この錯体Ａの^３１Ｐ－ＮＭＲ（^３１Ｐ－ＮＭＲ（１６２ＭＨｚ、ＣＤ_３ＣＮ））のチャートを図１に、^１Ｈ－ＮＭＲのチャートを図２に示した。５２．４ｐｐｍに鋭利なシングレットピークが観測できた。純度は１００％であった。 (Example 1)
(1) Synthesis Example 1: Complex A

300 mg (0.455 mmol) of (S,S)-N,N-bis[2-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine was weighed into a Schlenk tube, and 10 mL of acetonitrile was added. 115 mg (0.91 mmol) of iron chloride (2) dissolved in 2 mL of acetonitrile was added thereto at room temperature and stirred for 1 hour. After that, the solvent was distilled off leaving about 2 mL, and the residue was washed with 20 mL of ether. After washing, the solvent was completely distilled off, 15 mL of chloroform was added, and insoluble matter was removed with a glass filter. The recovered solution was completely dried and recrystallized with 5 mL of chloroform and 20 mL of hexane to obtain 211 mg of solid.
A ³¹ P-NMR ( ³¹ P-NMR (162 MHz, CD ₃ CN)) chart of this complex A is shown in FIG. 1, and a ¹ H-NMR chart is shown in FIG. A sharp singlet peak was observed at 52.4 ppm. Purity was 100%.

(2) Polymerization example Homopolymerization of ethylene Complex A (18 mg) was dissolved in 10 mL of toluene, and 20 mL of MMAO-3A/hexane solution (Al = 5.9 wt%) was added thereto and stirred at 25°C for 5 minutes to obtain a complex. The solution was adjusted. 1000 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 60°C. The pressure was increased to 2.5 MPa with ethylene. The previously prepared complex solution was injected therein with _N2 . The ethylene pressure was maintained at 2.5 MPa for 60 minutes, and ethanol was injected to terminate the polymerization. The resulting slurry was poured into hydrochloric acid/ethanol, filtered, washed with ethanol, and dried to obtain 0.2 g of polymer. The resulting polymer had a melting point of 135.1° C. and a weight average molecular weight of 2,477,000.

シュレンク管にＮ，Ｎ－ビス［ｏ－（ジフェニルホスフィノ）ベンジリデン］エチレンジアミンを３００ｍｇ（０．５０ｍｍｏｌ）量り取り、アセトニトリルを１１ｍＬ加えた。ここに、アセトニトリル３ｍＬに溶解させた塩化鉄（２）１２７ｍｇ（１．０ｍｍｏｌ）を室温で加え、３時間撹拌した。その後溶媒を１ｍＬ程度残して留去し、残留物にエーテル３０ｍＬを加えて沈殿物を析出させ、ガラスフィルターを用いて沈殿物を回収した。沈殿物をクロロホルム１５ｍＬで洗浄した後、クロロホルム１．２ｍＬとヘキサン６ｍＬで再結晶することで１１４ｍｇの固体（錯体Ｂ）を得た。
この錯体Ｂの^３１Ｐ－ＮＭＲ（^３１Ｐ－ＮＭＲ（１６２ＭＨｚ、ＣＤ_３ＣＮ））のチャートを図３に、^１Ｈ－ＮＭＲのチャートを図４に示した。^３１Ｐ－ＮＭＲからは５３．５ｐｐｍに鋭利なシングレットピークが観測された。錯体以外のピークが観測されないことから、今回準備された錯体が高純度であることが確認できた。純度は１００％であった。 (Example 2)
(1) Synthesis Example 2: Complex B

300 mg (0.50 mmol) of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine was weighed into a Schlenk tube, and 11 mL of acetonitrile was added. 127 mg (1.0 mmol) of iron chloride (2) dissolved in 3 mL of acetonitrile was added thereto at room temperature and stirred for 3 hours. After that, the solvent was distilled off leaving about 1 mL of the solvent, and 30 mL of ether was added to the residue to deposit a precipitate, which was recovered using a glass filter. The precipitate was washed with 15 mL of chloroform and then recrystallized with 1.2 mL of chloroform and 6 mL of hexane to obtain 114 mg of solid (complex B).
The ³¹ P-NMR ( ³¹ P-NMR (162 MHz, CD ₃ CN)) chart of this complex B is shown in FIG. 3, and the ¹ H-NMR chart is shown in FIG. A sharp singlet peak was observed at 53.5 ppm from ³¹ P-NMR. Since no peaks other than those of the complex were observed, it was confirmed that the complex prepared this time had high purity. Purity was 100%.

(2) Polymerization Example Ethylene Homopolymerization Ethylene polymerization was carried out in the same manner as in Example 1 (2) Polymerization Example, except that the complex used was changed to Complex B. The polyethylene obtained was 0.84 g. The weight average molecular weight of the resulting polymer was 539,000.

(Comparative example 1)
An Fe(II) complex having a pyridyldiimine ligand described in Non-Patent Document 2 was synthesized according to Non-Patent Document 2. ¹ H-NMR measurement of the obtained complex was attempted, but it was not possible due to magnetism, and the purity of the complex could not be determined by NMR measurement.
(Comparative example 2)
An Fe(III) complex with a bisoxazolidylphenylamine ligand described in Example 1 in US Pat. ¹ H-NMR measurement of the obtained complex was attempted, but it was not possible due to magnetism, and the purity of the complex could not be determined by NMR measurement.

Claims (5)

A method for producing an olefin polymer, comprising the step of polymerizing an olefin monomer using a catalyst containing a complex having a metal atom of group 8 or 9 of the periodic table in a low spin state as a polymerization catalyst component. 2. The method for producing an olefin polymer according to claim 1, wherein the complex has a tridentate or tetradentate ligand having a phosphorus atom as a coordination site. 3. The method for producing an olefin polymer according to claim 1, wherein the complex is represented by the following general formula (1).

[In general formula (1),
M is iron with an oxidation number of +2, ruthenium with an oxidation number of +2, cobalt with an oxidation number of +1 or rhodium with an oxidation number of +1;
n represents an integer of 0 or 1,
R ^1a , R ^1b , R ^1c and R ^1b each independently represent a hydrocarbon group having 3 to 12 carbon atoms,
R ^2a and R ^2b each independently represent a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms,
R ^3a , R ^3b , R ^3c , R ^3d , R ^3e , R ^3f , R ^3g and R ^3h each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 to 4 alkoxy 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 hydrocarbon group having 1 to 30 carbon atoms substituted with represents a substituent selected from the group consisting of silyl groups,
R ^4a and R ^4b each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, or R ^4a and R ^4b are linked to each other to form a ring,
L ¹ and L ² each independently represent a metal ancillary ligand selected from neutral monodentate ligands or anionic monodentate ligands;
X is absent or is a -1 or -2 counter anion species. ] 4. The method for producing an olefin polymer according to claim 3, wherein M is iron with an oxidation number of +2 or ruthenium with an oxidation number of +2. 5. The method for producing an olefin polymer according to any one of claims 1 to 4, wherein the weight average molecular weight of the obtained olefin polymer is 100,000 or more and 10,000,000 or less. A method for producing an olefin polymer.

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