JP2024056642A - Metal complex, olefin polymerization catalyst component and olefin polymerization catalyst which comprise that metal complex, and production method of olefin polymer using that olefin polymerization catalyst - Google Patents

Abstract

To provide a new metal complex from which high molecular weight polypropylene polymers can be obtained with high activity.SOLUTION: The metal complex is a reaction product of a compound represented by the general formula [1] or [2] in the figure and a transition metal compound comprising nickel or palladium.SELECTED DRAWING: None

Description

The present invention relates to a metal complex useful for producing olefin polymers and copolymers, an olefin polymerization catalyst component and an olefin polymerization catalyst using the metal complex, and a method for producing an olefin polymer using the olefin polymerization catalyst.

Copolymers of olefins and polar group-containing vinyl monomers are industrially useful polymers. These copolymers are generally produced by high-pressure radical polymerization. However, although high-pressure radical polymerization is effective for polymerizing ethylene, it cannot polymerize olefins with a large number of carbon atoms, such as propylene.

Coordination polymerization is also widely known as a method for producing ethylene or olefin polymers.
In coordination polymerization, Ziegler catalysts and metallocene catalysts are widely used, but these catalysts are deactivated by polar group-containing vinyl monomers, so it has been difficult to obtain copolymers with polar groups introduced by coordination polymerization using these catalysts.

In recent years, it has become clear that in the coordination polymerization of ethylene and a polar group-containing vinyl monomer, the use of a late transition metal complex catalyst reduces the deactivation caused by the polar group-containing vinyl monomer and allows the copolymerization to proceed. Specific examples include a palladium complex having a diimine ligand reported by Brookhart et al. (Non-Patent Document 1) and a nickel complex having a salicylaldimine ligand reported by Grubbs et al. (Non-Patent Document 2). It has also been disclosed that a nickel complex having a phosphinophenolate ligand can be applied to the copolymerization of ethylene and (meth)acrylate (Patent Document 1).

Compared to ethylene, there are only a limited number of reports on the polymerization of olefins such as propylene using late transition metal complex catalysts. For example, it has been disclosed that nickel complexes having phosphinophenolate ligands are useful for producing polypropylene with a relatively high molecular weight (Patent Document 2).

Patent No. 6913051 International Publication No. 2018/021446

M. Brookhart et al., J. Am. Chem. Soc., 1996, 118, 267-268. R. H. Grubbs et al. , "Science", 2000, 287, 460-462.

When industrially producing a copolymer of an olefin having 3 or more carbon atoms, such as propylene, and a polar group-containing vinyl monomer, the catalytic activity of the metal complex disclosed in Patent Document 2 is insufficient, and there is a demand for the development of a more active complex catalyst. At the same time, it is required for the polymer properties that the resulting polymer has a high molecular weight.

In view of the problems of the above-mentioned conventional techniques, the present invention aims to provide a novel metal complex, catalyst component, and olefin polymerization catalyst that are used to produce highly active polymers with higher molecular weights, and a method for producing olefins, particularly propylene polymers and copolymers, using the same.

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that when a novel metal complex which is a reaction product between a ligand having two non-aromatic hydrocarbon groups, hydrocarbon-group-substituted amino groups or hydrocarbon-group-substituted silyl groups on ^E1 capable of bonding to a transition metal and a phenyl group having a specific substituent at the ortho position of ^X1 capable of bonding to a transition metal, which is a compound represented by general formula [1] or [2], and a transition metal compound containing nickel or palladium is used as a catalyst component, polymerization of olefins, particularly propylene, proceeds with high activity and the molecular weight is significantly improved, which led to the completion of the present invention.

That is, the present invention includes the following aspects.
<1> A metal complex which is a reaction product between a compound represented by the following general formula [1] or [2] and a transition metal compound containing nickel or palladium:

[In formula [1] and formula [2],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
Z ¹ represents a hydrogen atom or a leaving group, and m represents the valence of Z ¹ .

<2> A metal complex represented by the following general formula [3].

[In formula [3],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
M represents nickel or palladium.
^L1 represents a ligand coordinated to M.
^R13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. ^R13 and ^L1 may be bonded to each other to form a ring.

<3> The metal complex according to <1> or <2>, wherein at least one of ^R4 and ^R8 is each independently (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which optionally has at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, or (vi) ^OR11 , ^SR11 , or ^NR11 ( ^R12 ).
<4> The metal complex according to <1> or <2>, wherein at least one of ^R4 and ^R8 is independently (v) an alkyl group having 1 to 20 carbon atoms, optionally having at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or an aryl group having 6 to 12 carbon atoms.
<5> The metal complex according to any one of <1> to <4>, wherein E ¹ is a phosphorus atom.
<6> The metal complex according to any one of <1> to <5>, wherein X ¹ is an oxygen atom.
<7> The metal complex according to any one of <2> to <6> above, wherein M is nickel.

<8> A catalyst component for olefin polymerization, comprising the metal complex according to any one of <1> to <7>.
<9> A catalyst component for olefin polymerization, comprising the metal complex according to any one of <2> to <7>.

<10> An olefin polymerization catalyst comprising a reaction product of a compound represented by the following general formula [1] or [2] and a transition metal compound containing nickel or palladium.

[In formula [1] and formula [2],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
Z ¹ represents a hydrogen atom or a leaving group, and m represents the valence of Z ¹ .

<11> The olefin polymerization catalyst according to <10>, wherein at least one of ^R4 and ^R8 is each independently (v) an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, optionally having at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, or (vi) ^OR11 , ^SR11 , or ^NR11 ( ^R12 ).
<12> The olefin polymerization catalyst according to <10> above, wherein at least one of ^R4 and ^R8 is each independently (v) an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, optionally having at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.
<13> The olefin polymerization catalyst according to any one of the above items <10> to <12>, wherein E ¹ is a phosphorus atom.
<14> The olefin polymerization catalyst according to any one of <10> to <13>, wherein X ¹ is an oxygen atom.
<15> An olefin polymerization catalyst comprising the olefin polymerization catalyst component according to <9>.

<16> A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin having 3 or more carbon atoms in the presence of the olefin polymerization catalyst according to any one of <10> to <15>.
<17> The method for producing an olefin polymer according to <16>, wherein the olefin is propylene.

According to the present invention, it is possible to provide a novel metal complex, catalyst component, and olefin polymerization catalyst which are used for producing olefins, particularly propylene polymers and copolymers, and which give polymers with high activity and higher molecular weights, as well as a method for producing olefins, particularly propylene polymers and copolymers, using the same.
According to the present invention, it is possible to produce a high molecular weight propylene polymer and a copolymer of propylene and a polar group-containing vinyl monomer with high activity. In addition, since the olefin polymerization catalyst of the present invention has higher activity than existing catalysts, it is possible to efficiently produce a polymer with a small amount of catalyst.

The present invention provides a metal complex which is a reaction product of a compound represented by general formula [1] or [2] and a transition metal compound containing nickel or palladium, a metal complex represented by general formula [3], an olefin polymerization catalyst component containing the metal complex, a catalyst containing the metal complex as a catalyst component, and a process for producing an olefin polymer or copolymer in the presence of the catalyst.
In the present invention, the term "polymerization" refers collectively to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and when there is no need to distinguish between the two, they are collectively referred to simply as "polymerization." In addition, in the present invention, the term "(meth)acrylic acid ester" includes both acrylic acid ester and methacrylic acid ester.
In addition, in this specification, the use of "to" indicating a range of values is used to mean that the values before and after it are included as the lower limit and upper limit.
In this specification, "Me" is methyl, "Et" is ethyl, "Pr" is propyl, "Bu" is butyl, "Cy" is cyclohexyl, "Ph" is phenyl, "4-MeOPh" is 4-methoxyphenyl, "OMe" is methoxy, "OEt" is ethoxy, "OiPr" is isopropoxy, "SMe" is methylthio, " _NMe2 " is dimethylamino, " _NEt2 " is diethylamino, and " _SiMe3 " is trimethoxysilyl.
Furthermore, in the prefixes of structural isomers of alkyl groups, "i" stands for iso, "n" stands for normal, "s" stands for secondary, and "t" stands for tertiary. When no prefix of structural isomer is given to an alkyl group, it indicates a normal structure.

1. Metal Complex The metal complex of the present invention is a reaction product between a compound represented by the following general formula [1] or [2] and a transition metal compound containing nickel or palladium.

[In formula [1] and formula [2],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
Z ¹ represents a hydrogen atom or a leaving group, and m represents the valence of Z ¹ .

The reaction product of the compound represented by the general formula [1] or [2], which is the metal complex of the present invention, and a transition metal compound containing nickel or palladium, can be obtained, for example, by contacting the compound represented by the general formula [1] or [2] with a transition metal compound containing nickel or palladium.
In the present invention, "contact" means that the compound represented by the general formula [1] or [2] and the transition metal compound are present in sufficient proximity so that ^E1 in the general formula [1] or [2] can form a coordinate bond with the transition metal and/or ^X1 in these general formulas can form a single bond with the transition metal. And, contacting the compound represented by the general formula [1] or [2] and the transition metal compound means mixing these compounds so that these compounds are present in sufficient proximity to each other and at least one of the two types of bonds can be formed.
The conditions for mixing the compound represented by the general formula [1] or [2] and the transition metal compound are not particularly limited. These compounds may be mixed directly or in a solvent. In particular, it is preferable to use a solvent in order to achieve uniform mixing.
In the obtained metal complex, the compound represented by the general formula [1] or [2] serves as a ligand, and therefore the reaction between the compound represented by the general formula [1] or [2] and the transition metal compound is usually a ligand exchange reaction. When the obtained metal complex is more thermodynamically stable than the transition metal compound, the ligand exchange reaction proceeds by mixing the compound represented by the general formula [1] or [2] and the transition metal compound at room temperature (15 to 30° C.). On the other hand, when the obtained metal complex is more thermodynamically unstable than the transition metal compound, it is preferable to appropriately heat the mixture in order to sufficiently proceed with the ligand exchange reaction.

The metal complex obtained by contacting the compound represented by the general formula [1] or [2] with a transition metal compound containing nickel or palladium is presumed to have a structure represented by the general formula [3] described later.
However, since the compound represented by the general formula [1] or [2] is a bidentate ligand, when the compound is contacted with a transition metal compound containing nickel or palladium, a metal complex having a structure other than that represented by the general formula [3] may be generated. For example, only X ¹ in the general formula [1] or [2] may form a bond with the transition metal, or only E ¹ in these formulas may form a bond with the transition metal. In addition, although the metal complex represented by the general formula [3] is a 1:1 reaction product of the compound represented by the general formula [1] or [2] and the transition metal compound, it is also possible to obtain a reaction product with a different composition ratio depending on the type of transition metal compound. For example, it is also possible that two or more molecules of the compound represented by the general formula [1] or [2] form a complex with one transition metal, or that one molecule of the compound represented by the general formula [1] or [2] reacts with two or more transition metals to form a polynuclear complex.
Therefore, the metal complex of the present invention may be a mixture containing two or more reaction products, or may be a metal complex composition.
In the present invention, it is not denied that a metal complex having a structure other than that represented by the general formula [3] can be used for producing an olefin (co)polymer, similarly to the metal complex represented by the general formula [3].

By using the metal complex of the present invention, it is possible to obtain olefin (co)polymers with high activity and higher molecular weights, in particular propylene (co)polymers with higher molecular weights, with high activity.
It is believed that the catalyst has two non-aromatic hydrocarbon groups on ^E1 capable of forming a coordinate bond with M, which is a central metal thought to be an active site in an olefin polymerization catalyst, and also has a phenyl group having a specific substituent at the ortho position of ^X1 capable of forming a covalent bond with M, and therefore the steric congestion around M is appropriately controlled, resulting in high activity, and also suppression of β-hydrogen elimination, thereby improving the molecular weight of the resulting polymer chain.
It is presumed that due to these synergistic effects, the use of the metal complex of the present invention makes it possible to obtain an olefin (co)polymer with higher activity and higher molecular weight.

R ¹ to R ¹⁰ , E ¹ , and X ¹ in general formulas [1] and [2], as well as Z and m in general formula [1] will be explained below.

R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.

(ii) Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Of these, fluorine atoms are preferred.

In (iii), examples of the hydrocarbon group having 1 to 30 carbon atoms include linear, branched, and cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 30 carbon atoms, branched non-cyclic alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, and arylalkyl groups having 7 to 30 carbon atoms; alkenyl groups having 2 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, including cycloalkenyl groups having 3 to 30 carbon atoms which may have a side chain; aryl groups having 6 to 30 carbon atoms, and aryl groups having 6 to 30 carbon atoms, including alkylaryl groups having 7 to 30 carbon atoms.

Examples of linear alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups, and may be linear alkyl groups having 1 to 10 carbon atoms.

Examples of branched acyclic alkyl groups having 3 to 30 carbon atoms include i-propyl, i-butyl, t-butyl, s-butyl, i-pentyl (3-methylbutyl), t-pentyl (1,1-dimethylpropyl), s-pentyl (1-methylbutyl), 2-methylbutyl, neopentyl (2,2-dimethylpropyl), 1,2-dimethylpropyl, i-hexyl (4-methylpentyl), and 2-heptyl groups, and may be branched acyclic alkyl groups having 3 to 8 carbon atoms.

Examples of cycloalkyl groups that may have a side chain having 3 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, cycloheptyl, cyclooctyl, decahydronaphthyl (bicyclo[4,4,0]decyl), 5-tricyclo[3.3.1.13,7]dec-1-yl (1-adamantyl), 5-methyl-2-(propan-2-yl)cyclohexyl (menthyl), and bicyclo[2.2.1]hept-2-yl groups. They may be cycloalkyl groups that may have a side chain having 3 to 10 carbon atoms, or cycloalkyl groups that may have a side chain having 3 to 6 carbon atoms.

Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, phenethyl (2-phenylethyl), 9-fluorenyl, naphthylmethyl, and 1-tetralinyl groups. They may be arylalkyl groups having 7 to 15 carbon atoms or arylalkyl groups having 7 to 10 carbon atoms.

Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a styryl group, and a cinnamyl group. The alkenyl group may have 3 to 8 carbon atoms, or may have 4 to 8 carbon atoms.
Examples of the cycloalkenyl group which may have a side chain having 3 to 30 carbon atoms include a cyclopentenyl group, a cyclohexenyl group, and a bicyclo[2.2.1]hept-5-en-2-yl group. It may be a cycloalkenyl group which may have a side chain having 3 to 10 carbon atoms, or it may be a cycloalkenyl group which may have a side chain having 5 to 7 carbon atoms.

Examples of aryl groups having 6 to 30 carbon atoms include phenyl, naphthyl, azulenyl, biphenyl, anthracenyl, terphenyl, phenanthrenyl, triphenylenyl, chrysenyl, pyrenyl, and tetracenyl groups. They may be aryl groups having 6 to 18 carbon atoms or aryl groups having 6 to 12 carbon atoms.

The alkylaryl group having 7 to 30 carbon atoms may be an aryl group substituted with one or more linear or branched acyclic alkyl groups having 1 to 10 carbon atoms, for example, an alkylaryl group in which at least one of the linear alkyl groups having 1 to 10 carbon atoms and the branched acyclic alkyl groups having 3 to 10 carbon atoms is substituted with the aryl group having 6 to 18 carbon atoms, or an alkylaryl group in which at least two of the linear alkyl groups having 1 to 10 carbon atoms and the branched acyclic alkyl groups having 3 to 10 carbon atoms are substituted with the aryl group having 6 to 18 carbon atoms. Specific examples of the alkylaryl group having 7 to 30 carbon atoms include alkylaryl groups having 7 to 20 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl.

Examples of the heteroatom used in (iii) include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, a selenium atom, a silicon atom, a halogen atom, and a boron atom. Among these heteroatoms, a fluorine atom and a chlorine atom are preferred.
Specific examples of the "group containing a heteroatom" used in (iii) include the same groups as those in the heteroatom-containing substituent (iv) described below. Examples of the "group containing a heteroatom" include an alkoxy group (OR ¹¹ ) and an alkoxycarbonyl group (CO ₂ R ¹¹ ). R ¹¹ is as described below.

In the above (iii), the total number of carbon atoms of the substituents corresponding to R ¹ , R ² or R ³ may preferably have an upper limit of 30 or less, 25 or less, 20 or less, or 15 or less. The lower limit of the total number of carbon atoms may preferably be 1 or more, 2 or more, or 4 or more.
In light of the above, (iii) "a specific group which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom" refers to (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an arylalkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms, (iii-B) a group in which each of the groups in (iii-A) is substituted with one or more of the heteroatoms, (iii-C) a group in which each of the groups in (iii-A) is substituted with one or more of the "groups containing a heteroatom", and (iii-D) a group in which each of the groups in (iii-A) is substituted with one or more of the heteroatoms and is substituted with one or more of the "groups containing a heteroatom". Examples of (iii-C) include an alkyl group substituted with an alkoxy group, an aryl group substituted with an alkoxy group, an aryl group substituted with an alkoxycarbonyl group, and an aryl group substituted with an acyloxy group.

(iv) The heteroatom-containing substituent specifically refers to OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In the present invention, the hydrocarbon group includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons, and examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned linear alkyl groups, branched non-cyclic alkyl groups, cycloalkyl groups which may have a side chain, arylalkyl groups, alkenyl groups, aryl groups, and alkylaryl groups, each having 1 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon groups of R ¹¹ and R ¹² may be 1 to 10, 1 to 6, or 1 to 4. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium, or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2.

Preferred examples of R ¹ , R ² and R ³ each independently include: (i) a hydrogen atom; (ii) a fluorine atom, a chlorine atom, or a bromine atom; (iii) a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, a phenyl group, a trifluoromethyl group, a pentafluorophenyl group, a naphthyl group, or an anthracenyl group; and (iv) a methoxy group, an ethoxy group, a phenoxy group, a nitrile group, a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, a trimethylsilyloxy group, a trimethoxysiloxy group, a cyclohexylamino group, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, or the like.
Among these, particularly preferred are (i) a hydrogen atom; (iii) a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, a trifluoromethyl group; and (iv) a methoxy group, a trimethylsilyl group, a trimethylsilyloxy group, a cyclohexylamino group, and the like.
Among these, from the viewpoint of effectively controlling the electron density of M, ^R2 is preferably a hydrogen atom, a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, or a trifluoromethyl group, and may be a hydrogen atom, a methyl group, or a trifluoromethyl group.

Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom selected from the group consisting of oxygen, nitrogen and sulfur. In this case, the number of ring members is 5 to 8, and the ring may or may not have a substituent. The substituent may be at least one of the above (ii), (iii) and (iv).

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ).
However, at least one of R ⁴ to R ⁸ is other than a hydrogen atom. That is, at least one of R ⁴ to R ⁸ is (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ).

(v) the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a ^heteroatom , may be ^a linear alkyl group having 1 to 20 carbon atoms, a branched non-cyclic alkyl group having 3 to 120 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. These are included in the above (iii) and may be the same as those explained in the above (iii).
In particular, (v) in R ⁴ to R ⁸ may be, from the viewpoint of controlling the steric crowding around M, a linear alkyl group having 1 to 12 carbon atoms, a branched acyclic alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 7 to 12 carbon atoms, or an aryl group substituted with at least one OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ), or may be a linear alkyl group having 1 to 6 carbon atoms, a branched acyclic alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms which may have a side chain, an aryl group having 6 to 12 carbon atoms, or an aryl group substituted with at least one OR ^{11 '} (wherein R ^{11 '} is an alkyl group having 1 to 6 carbon atoms).
(v) in R ⁴ to R ⁸ may be, among others, a methyl group, an ethyl group, an i-propyl group, an i-butyl group, a t-butyl group, a s-butyl group, a cyclohexyl group, an adamantyl group, a phenyl group, or a 4-methoxyphenyl group.

(vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ) in R ⁴ to R ⁸ is included in the above (iv) and may be the same as that explained in the above (iv).
(vi) in R to ^R may be, among others, OR ^11' , SR ^11' , or NR ^11' (R ^12' ) (wherein R ^11' is an alkyl group having 1 to 6 carbon atoms, and R ^{12 '} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), or OR ^11" , SR ^11" , or NR ^11" (R ^12" ) (wherein R ^11" is an alkyl group having 1 to 4 carbon atoms, and R ^12" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
(vi) in R ⁴ to R ⁸ may be, among others, a methoxy group, an ethoxy group, an i-propoxy group, a methylthio group, or a dimethylamino group.

The substituents other than hydrogen atoms in R ⁴ to R ⁸ may be electron-donating groups so as not to reduce the electron density of the coordinated transition metal atom.

At least one of R ⁴ and R ⁸ may each independently be (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ), and may further be (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.
It is preferable that R ⁴ and R ⁸ are each independently (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ), and more preferably (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.

When at least one of R ⁴ and R ⁸ is other than a hydrogen atom, R ⁵ and R ⁷ may be a hydrogen atom.
When at least one of R ⁴ and R ⁸ is other than a hydrogen atom, R ⁶ may be (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ), which may be (i) a hydrogen atom, or (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.

When R ⁴ and R ⁸ are hydrogen atoms, among others, R ⁶ may be other than a hydrogen atom, and R ⁶ may be (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ), and (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.
When R ⁴ and R ⁸ are hydrogen atoms, R ⁵ and R ⁷ may be other than hydrogen atoms.

R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
Here, examples of non-aromatic hydrocarbon groups include linear, branched and cyclic aliphatic hydrocarbon groups, and combinations thereof, such as linear alkyl groups having 1 to 30 carbon atoms, branched non-cyclic alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, alkenyl groups having 2 to 30 carbon atoms, and cycloalkenyl groups having 3 to 30 carbon atoms which may have a side chain.
The hydrocarbon groups in ^R9 and ^R10 which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms may be the same as those described in (iii) above.

R ⁹ and R ¹⁰ are in the vicinity of M and exert steric and/or electronic interactions with M. In order to exert such effects, R ⁹ and R ¹⁰ are preferably bulky.
The number of carbon atoms in each of the linear alkyl group, the branched noncyclic alkyl group, the cycloalkyl group which may have a side chain, the alkenyl group, and the cycloalkenyl group which may have a side chain is preferably 3 or more and 25 or less, more preferably 4 or more, and may be 7 or more, 10 or more, 20 or less, or 15 or less.

Among the examples of R ⁹ and R ¹⁰ , the linear alkyl group includes linear alkyl groups having 3 to 15 carbon atoms, such as n-propyl, n-butyl, n-pentyl, and n-hexyl groups.
Among the examples of R ⁹ and R ¹⁰ , the branched non-cyclic alkyl group includes a branched non-cyclic alkyl group having 3 to 15 carbon atoms, such as an isopropyl group, an isobutyl group, a pentan-2-yl group, a pentan-3-yl group, a 3-methyl-2-pentyl group, a 2-methyl-3-pentyl group, a t-butyl group, a t-pentyl group (1,1-dimethylpropyl group), a 2-methyl-2-pentyl group, a 3-methyl-3-pentyl group, a t-hexyl group (1,1-dimethylbutyl group), and the like. Among these, a branched non-cyclic alkyl group having 4 to 6 carbon atoms is preferred.
Among the examples of R ⁹ and R ¹⁰ , the cycloalkyl group which may have a side chain includes a cycloalkyl group having 3 to 15 carbon atoms which may have a side chain, such as a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1,2-dimethylcyclobutyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a 5-tricyclo[3.3.1.1 ^3,7 ]dec-1-yl group (a 1-adamantyl group), a 5-methyl-2-(propan-2-yl)cyclohexyl group (a menthyl group), a bicyclo-[2.2.1]-hept-2-yl group, and the like. Among these, a cycloalkyl group which may have a side chain and has 6 to 12 carbon atoms is preferred.
Among the examples of R ⁹ and R ¹⁰ , the alkenyl group may be an alkenyl group having 4 to 10 carbon atoms, such as a butenyl group, a pentenyl group, or a hexenyl group.
Among the examples of ^R9 and ^R10 , the cycloalkenyl group which may have a side chain may be a cycloalkenyl group having 3 to 15 carbon atoms which may have a side chain, such as a cyclopentenyl group, a cyclohexenyl group, a bicyclo[2.2.1]hept-5-en-2-yl group, and among these, a cycloalkenyl group which may have a side chain having 5 to 10 carbon atoms is preferred.

Among the examples of R ⁹ and R ¹⁰ , NR ¹¹ (R ¹² ) may, for example, be a dimethylamino group, a diethylamino group, or a cyclohexylamino group.
Furthermore, among the examples of R ⁹ and R ¹⁰ , examples of SiR ¹¹ (R ¹² ) ₂ include a trimethylsilyl group and a triethylsilyl group.

Of these, preferred as R ⁹ and R ¹⁰ are t-butyl, t-pentyl (1,1-dimethylpropyl), 2-methyl-2-pentyl, 3-methyl-3-pentyl, 1-methylcyclopentyl, 1-adamantyl, menthyl, diethylamino, and trimethylsilyl groups, and more preferred among these are t-butyl, 1-adamantyl, and menthyl.

E ¹ represents a phosphorus atom, an arsenic atom, or an antimony atom. Among these, E ¹ is preferably a phosphorus atom in terms of its coordination power to metals.
^X1 represents an oxygen atom or a sulfur atom. Among these, ^X1 is preferably an oxygen atom from the viewpoint of acidity for deprotonation.
Z represents a hydrogen atom or a leaving group. Specific examples of Z include a hydrogen atom, a halogen atom, an R ¹¹ SO ₂ group (wherein R ¹¹ is as defined above), and a CF ₃ SO ₂ group. The halogen atom may be a bromine atom or an iodine atom, and specific examples of the R ¹¹ SO ₂ group include a tosyl group (p-toluenesulfonyl group) and a mesyl group (methanesulfonyl group).
m represents the valence of Z.

The general formula [2] is expressed in the form of an anion, but any counter cation can be used as long as it does not inhibit the reaction with the transition metal compound in the present invention. Specific examples of the counter cation include ammonium, quaternary ammonium or phosphonium, and metal ions of Groups 1 to 14 of the periodic table. Among these, preferred are NH ₄ ⁺ , R ¹¹ ₄ N ⁺ (wherein R ¹¹ is as described above, and the four R ¹¹ may be the same or different. The same applies below.), R ¹¹ ₄ P ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , and Al ³⁺ , and more preferred are R ¹¹ ₄ N ⁺ , Li ⁺ , Na ⁺ , and K ⁺ .

Specific combinations of substituents in the general formulas [1] and [2] of the present invention are shown in Table 1 below. Z and m relate only to general formula [1]. However, specific examples are not limited to the following examples.

The compounds represented by the general formulas [1] and [2] can be synthesized according to known synthesis methods.

The transition metal compounds containing nickel or palladium used in the present invention are those capable of reacting with the compounds represented by general formula [1] or [2] to form complexes capable of polymerization. These are sometimes called precursors.

Among the transition metal compounds that can be used, examples of transition metal compounds containing nickel atoms include bis(1,5-cyclooctadiene)nickel(0) (hereinafter, Ni(COD) ₂ ), (N,N,N,N-tetramethylethylenediamine)nickeldimethyl(II) (hereinafter, (TMEDA)NiMe ₂ ), diacetylacetonatenickel(II) (hereinafter, Ni(acac) ₂ ), a complex represented by the general formula: Ni(CH ₂ CR ¹⁴ CH ₂ ) ₂ , bis(cyclopentadienyl)nickel(II), a complex represented by the general formula: Ni(CH ₂ Si(R ¹⁴ ) ₃ ) ₂ (L ¹ ) ₂ , and a complex represented by the general formula: Ni(R ^13' ) ₂ (L ¹ ) ₂ [wherein R ^13' represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to Ni, and L ¹ represents a ligand coordinated to Ni, and R ^13′ and L ¹ may be bonded to each other to form a ring. R ¹⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom, OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group (wherein R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2).

Specific examples of R ^13′ include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group.
In addition, when M is a nickel atom and is a zero-valent transition metal compound, R ^13′ may be a neutral ligand coordinated to M. The neutral ligand coordinated to M in R ^13′ is a neutral electron-donating ligand. One example is a hydrocarbon compound having 1 to 20 carbon atoms and a nitrogen atom, phosphorus atom, arsenic atom, oxygen atom, sulfur atom, selenium atom, or the like, which is an electrically neutral ligand that can form a coordinate bond by coordinating an unpaired electron to M. Another example is a hydrocarbon compound having a carbon-carbon unsaturated bond that may contain a heteroatom that can be coordinated to a transition metal, specifically, a compound such as ethylene or cyclooctadiene that forms a π-donor bond by donating a π electron, and a compound such as dibenzylideneacetone (dba) that has an unsaturated bond and a heteroatom that coordinates to a metal. Examples of these include acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, and other ligands known as neutral ligands for metal complexes, and ligands that donate π electrons, such as allyl and cyclopentadienyl.

The ligand ^L1 in the present invention is a hydrocarbon compound having 1 to 20 carbon atoms and having, as an atom capable of forming a coordinate bond, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, or a selenium atom having an unpaired electron. Alternatively, a hydrocarbon compound which may contain a heteroatom having a carbon-carbon unsaturated bond capable of coordinating to a transition metal may be used as ^L1 . The number of carbon atoms in ^L1 is preferably 1 to 16, and more preferably 1 to 10. As ^L1 which forms a coordinate bond with M in the general formula [3] described later, a compound having no electric charge is preferred.

Preferred examples of ^L1 in the present invention include cyclic unsaturated hydrocarbons, phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, amines, etc. More preferred examples of ^L1 include cyclic olefins, phosphines, pyridines, cyclic ethers, aliphatic esters, aromatic esters, and particularly preferred examples of ^L1 include trialkylphosphine, pyridine, lutidine (dimethylpyridine), ^picoline ( _{methylpyridine} ), and ^R11CO2R11 (the definition of ^R11 is as described above).
In addition, R ^13′ and L ¹ may be bonded to each other to form a ring, such as 1,5-cyclooctadiene or a π-allyl bond.
Further, the halogen atom in R ¹⁴ , the hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom, OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ¹² ) ₂ M', or the epoxy-containing group, can be as described above.

Among these transition metal compounds, those preferably used are Ni(COD) ₂ , NiPhCl(PEt ₃ ) ₂ , NiPhCl(PPh ₃ ) _{2 ,} NiPhCl(TMEDA) (hereinafter, TMEDA represents tetramethylethylenediamine), NiArBr(TMEDA) (wherein Ar is an aryl group, for example, 4-fluorophenyl), Ni(acac) ₂ , (TMEDA)NiMe ₂ , a complex represented by the general formula: Ni(CH ₂ CR ¹⁴ CH ₂ ) ₂ (wherein R ¹⁴ is as defined above), a complex represented by the general formula: Ni(CH ₂ Si(R ¹⁴ ) ₃ ) ₂ (L ¹ ) ₂ (wherein R ¹⁴ and L ¹ are as defined above), a complex represented by the general formula: Ni(R ^13′ ) ₂ (L ¹ ) ₂ (wherein R ^13′ and L ¹ are as defined above), Pd(dba) ₂ (hereinafter, dba represents dibenzylideneacetone), Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ , Pd(OCOCH ₃ ) ₂ , and (1,5-cyclooctadiene)PdMeCl.
Particularly preferred are Ni(COD) ₂ , NiPhCl( _PEt3 ) ₂ , NiPhCl( _PPh3 ) _2, NiPhCl(TMEDA), NiArBr(TMEDA), Ni(acac) ₂ , (TMEDA) _NiMe2 , Ni( _{CH2CHCH2 ) 2} , Ni( _CH2CMeCH2 ) ₂ , Ni( _CH2SiMe3 ) ₂ (Py) ₂ (hereinafter Py represents _pyridine ), Ni( _CH2SiMe3 ) ₂ (Lut) ₂ (hereinafter Lut represents 2,6 _- lutidine), _NiPh2 (Py) ₂ , _NiPh2 (Lut) ₂ , and Pd(dba) _{2 .} , Pd ₂ (dba) ₃ , Pd ₃ (dba) ₄ , Pd(OCOCH ₃ ) ₂ , (1,5-cyclooctadiene)PdMeCl.

The reaction product of the present invention can be obtained by contacting the compound represented by the above general formula [1] or [2] with the above transition metal compound (referred to as [4]), for example, [I] + [2]: [4] = 1:99 to 99:1 (molar ratio), in an organic solvent such as toluene or benzene at 0°C to 100°C under reduced pressure to pressure for 1 to 86,400 seconds. When a toluene or benzene solution of Ni(COD) ₂ is used as the transition metal compound, the generation of the reaction product can be confirmed by the change in color of the solution from yellow to, for example, red.

After this reaction, a part of the components constituting the transition metal compound other than the transition metal in the compound is replaced by the part excluding Z in general formula [1] or the compound of general formula [2], and a metal complex that is a reaction product of the compound represented by general formula [1] or [2] and the transition metal compound, such as a metal complex represented by the following general formula [3], is generated. It is preferable that this replacement reaction proceeds quantitatively, but in some cases it does not have to proceed completely. After the reaction is completed, in addition to the metal complex that is a reaction product of the compound represented by general formula [1] or [2] and the transition metal compound, such as a complex represented by general formula [3], other components derived from general formula [1], [2], and the transition metal compound may coexist, but these other components may or may not be removed when performing the polymerization reaction or copolymerization reaction of the present invention. In general, it is preferable to remove these other components because high activity can be obtained by removing these other components.

It is believed that the reaction product of the compound represented by the general formula [1] or [2] and a transition metal compound containing nickel or palladium contains a metal complex represented by the following general formula [3]. As a reaction product between a compound having a skeleton similar to that of the compound represented by the general formula [1] or [2] and a transition metal compound containing nickel or palladium, a structure of a metal complex having a skeleton similar to that of the metal complex represented by the following general formula [3] has been reported, and it has been reported that the metal complex exhibits catalytic activity (for example, ACS Macro Lett. 2018, 7, 213-217., Chem. Eur. J. 2003, 9, 6093-6107., European Journal of Inorganic Chemistry, 2000, 3, 431-440., J. Am. Chem. Soc. 2017, 139, 3611., etc.). Therefore, it is presumed from the reaction mechanism that the reaction product between the compound represented by the general formula [1] or [2] and a transition metal compound containing nickel or palladium contains a metal complex represented by the following general formula [3]. As described later, since the reaction product between the compound represented by the general formula [1] or [2] and a transition metal compound containing nickel or palladium exhibits excellent catalytic activity, it is presumed that the structure represented by the following general formula [3], which is presumed from the reaction mechanism, is one of the compounds exhibiting catalytic activity.
However, as described above, the structure of the metal complex that is the reaction product is not limited to only the structure represented by the general formula [3].

In producing a metal complex represented by the following general formula [3], a coordinating compound (L 1 ) or a covalent compound for substituting R ¹³ in the general formula [3] may be further present when reacting a compound represented by the general formula [ ¹ ] or [2] with a transition metal compound containing nickel or palladium.
When nickel or palladium is used as M in the present invention, the stability of the generated metal complex may be increased by the coexistence of a Lewis basic coordinating compound in the system. In such a case, the coexistence of the coordinating compound may be allowed as long as the coordinating compound does not inhibit the polymerization reaction or copolymerization reaction of the present invention.
The coordinating compound used in the present invention may be a hydrocarbon compound having 1 to 20 carbon atoms and having an oxygen atom, a nitrogen atom, a phosphorus atom, an arsenic atom, a sulfur atom, or a selenium atom as an atom capable of coordinating, or a hydrocarbon compound which may contain a heteroatom having a carbon-carbon unsaturated bond capable of coordinating to a transition metal, and may have the same meaning as ^L1 .

The covalent compound used in the present invention is a compound capable of substituting a ligand derived from a transition metal compound for R ¹³ in the general formula [3], and may be an organometallic compound. R ¹³ is incorporated into a polymer as an initiation terminal of the polymerization reaction and can greatly contribute to the initial rate of the polymerization reaction, and it is preferable to use a covalent compound for introducing R ¹³ in combination depending on the situation.
The covalent compound may be an organolithium compound, which may be R ^13″ Li (wherein R ^13″ is a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom), or an organolithium compound having a hydrocarbon group having 1 to 10 carbon atoms. Examples of the organolithium compound having a hydrocarbon group having 1 to 10 carbon atoms include methyllithium, n-butyllithium, and phenyllithium. Among these, methyllithium and phenyllithium are preferred, and methyllithium is more preferred.

The metal complex of the present invention is a metal complex represented by the following general formula [3]:

[In formula [3],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ¹² ) ₂ M′, or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M′ represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
M represents nickel or palladium.
^L1 represents a ligand coordinated to M.
^R13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. ^R13 and ^L1 may be bonded to each other to form a ring.]

In the general formula [3], R ¹ to R ¹⁰ , E ¹ and X ¹ may be the same as those explained in the general formula [1] or [2]. Thus, there is a commonality in the complex structure between the metal complex in the reaction product and the metal complex represented by the general formula [3] in terms of the main skeleton containing a benzene ring and these substituents (R ¹ to R ⁶ , E ¹ , X ¹ ).
Moreover, M and ^L1 in the general formula [3] are as explained in the transition metal compound.

In the present invention, R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
In a transition metal compound in which M is Ni and has a valence of zero, R ^13' may be a neutral ligand coordinated to M, but when a compound represented by the general formula [1] or [2] reacts with a transition metal compound in which M is Ni and has a valence of zero, Ni becomes divalent, and therefore R ¹³ after the reaction becomes an anionic ligand rather than a neutral ligand. For example, when a compound represented by the general formula [1] or [2] reacts with Ni(COD) ₂ , the ligand derived from the transition metal compound becomes a σ,π-cyclooct-4-enyl group in which R ¹³ and L ¹ are bonded to each other to form a ring.
The polymerization or copolymerization reaction in the present invention is believed to be initiated by the insertion of an olefin such as propylene or a copolymerizable monomer thereof into the bond between M and R ^13. Therefore, if R ¹³ has an excessively large number of carbon atoms, this initiation reaction tends to be inhibited. For this reason, R ¹³ preferably has 1 to 16 carbon atoms, excluding the number of carbon atoms contained in the substituent, and more preferably has 1 to 10 carbon atoms.
Specific examples of R ¹³ include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenyl group, and a p-methylphenyl group.
R ¹³ and L ¹ may be bonded to each other to form a ring, examples of which include a σ,π-cyclooct-4-enyl group and an acetylacetonate group, which are also preferred embodiments of the present invention.

Specific combinations of substituents and the like in the general formula [3] in the present invention are shown in Table 2 below. However, the specific examples are not limited to the following examples.

To help understand the structure of the metal complex, the structural formula of No. 4 in Table 2 above is shown below.

Also exemplified are compounds in which M in the compounds of complex numbers 1 to 45 exemplified in Table 2 is changed from Ni to Pd.

In the present invention, the reaction may be carried out in advance in a vessel separate from the reactor used for the polymerization of olefins such as propylene or the copolymerization of olefins and (meth)acrylic esters, and the resulting metal complex, which is the reaction product of the compound represented by general formula [1] or [2] and the transition metal compound, may be subjected to the polymerization of olefins such as propylene or the copolymerization of olefins and (meth)acrylic esters, or the reaction may be carried out in the presence of these monomers. The reaction may also be carried out in a reactor used for the polymerization of olefins such as propylene or the copolymerization of olefins and (meth)acrylic esters. In this case, these monomers may or may not be present. In addition, the components represented by general formulas [1] and [2] may each be used alone, or multiple types of components may be used in combination. In particular, such multiple types of combinations are useful for the purpose of widening the molecular weight distribution and the comonomer content distribution.

As described above, the compound represented by the general formula [1] or [2] is contacted with a transition metal compound containing nickel or palladium, and if necessary, the coordination compound or the covalent compound is further used to react the compound, thereby producing the metal complex of the present invention, which is the reaction product between the compound represented by the general formula [1] or [2] and the transition metal compound containing nickel or palladium, the metal complex represented by the general formula [3].

2. Catalyst Component for Olefin Polymerization The catalyst component for olefin polymerization of the present invention is characterized by containing the above-mentioned metal complex of the present invention.
In the present invention, the metal complex of the present invention can be used as a catalyst component for the polymerization or copolymerization of olefins. As described above, the metal complex of the present invention can be produced by the reaction of a compound represented by the general formula [1] or [2] with a transition metal compound. When the metal complex of the present invention is used as a catalyst component, it may be used as a reaction solution as it is, may be used after isolation, or may be used after being supported on a carrier. Supporting on a carrier may be performed in a reactor used for the polymerization of olefins or the copolymerization of olefins and (meth)acrylic acid esters in the presence or absence of these monomers, or may be performed in a vessel separate from the reactor.

Any carrier can be used as long as it does not impair the gist of the present invention. In general, inorganic oxides and polymer carriers can be used. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and the like or mixtures thereof can be mentioned, and mixed oxides such as SiO ₂ -Al ₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO ₂ -MgO, and SiO ₂ -Cr ₂ O ₃ can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, and polyimide carriers can be used. There are no particular limitations on the particle size, particle size distribution, pore volume, specific surface area, etc. of these carriers, and any carrier can be used.

As the inorganic silicate, clay, clay minerals, zeolite, diatomaceous earth, etc. can be used. These may be synthetic products or naturally occurring minerals. Specific examples of clay and clay minerals include allophane group such as allophane, kaolin group such as dickite, nacrite, kaolinite, anoxite, halloysite group such as metahaloysite, halloysite, serpentine group such as chrysotile, lizardite, antigorite, smectite such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, glauconite, attapulgite, sepiolite, pyrogorskite, bentonite, kibushi clay, gairome clay, hisingerite, pyrophyllite, ryokudeite group, etc.
These may form a mixed layer. Examples of artificially synthesized substances include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, etc. Among these specific examples, preferred are kaolin group such as dickite, nacrite, kaolinite, anoxite, etc., halloysite group such as metahaloysite, halloysite, etc., serpentine group such as chrysotile, lizardite, antigorite, etc., smectite such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, glauconite, etc., synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, etc., and particularly preferred are smectite such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite.

These carriers may be used as they are, or may be treated with an acid such as hydrochloric acid, nitric acid, or sulfuric acid, and/or a salt such as LiCl, NaCl, KCl, _CaCl2 , _MgCl2 , _Li2SO4 , _MgSO4 , _ZnSO4 , Ti( _SO4 ) ₂ , Zr( _SO4 ) ₂ , or _Al2 ( _SO4 ) _{3 .} In this treatment, the corresponding acid and base may be mixed to generate a salt in the reaction system. Also, shape control such as pulverization or granulation, or drying treatment may be performed.

3. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is characterized by containing the following component (A) and, optionally, component (B).
Component (A): The metal complex of the present invention; Component (B): An organoaluminum compound;

Component (A) is the metal complex of the present invention, and only one type of metal complex may be used, or two or more types of metal complexes may be used in combination.

An example of the organoaluminum compound used as component (B) is represented by the following general formula:
Al( ^Rp ) _{aX (3-a)}
In the general formula, R ^p is a hydrocarbon group having 1 to 20 carbon atoms, X is a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group, and a is a number greater than 0 and less than or equal to 3.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and tri-normal-octylaluminum, and halogen atom- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide.

Of these, triisobutylaluminum or tri-normal octylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination. The above aluminum compounds may be modified with alcohol, phenol, or the like. Examples of these modifying agents include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, and 2,6-di-t-butylphenol, with preferred examples being 2,6-dimethylphenol and 2,6-di-t-butylphenol.

In the method for preparing the olefin polymerization catalyst according to the present invention, the method for contacting component (A) and component (B) is not particularly limited.
The contact may be carried out not only during the preparation of the catalyst but also during the prepolymerization with an olefin or during the polymerization of an olefin.
The contact of the above components (A) and (B) is preferably carried out in an inert gas such as nitrogen, in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, etc. 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.

4. Method for Producing Olefin Polymer One embodiment of the method for producing an olefin polymer of the present invention involves polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention.
One embodiment of the method for producing an olefin polymer of the present invention may be a method for producing an olefin polymer, in which an olefin having 3 or more carbon atoms is polymerized or copolymerized in the presence of the olefin polymerization catalyst of the present invention.
The olefin in the present invention is represented by the general formula: CH ₂ ═CHR ^20. Here, R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring, and/or an unsaturated bond. If the carbon number of R ²⁰ is more than 20, sufficient polymerization activity tends not to be exhibited. Therefore, among them, preferred olefins include olefins in which R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
More preferred olefins include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, vinylcyclohexene, and styrene. A single olefin may be used, or a plurality of olefins may be used in combination.
In the process for producing an olefin polymer and a process for producing an olefin copolymer of the present invention, it is preferable that the polymer contains an olefin having 3 or more carbon atoms, and it is particularly preferable that the olefin is propylene.

Another embodiment of the method for producing an olefin polymer of the present invention is to copolymerize (a) an olefin with (b) a (meth)acrylic acid ester monomer, a vinyl monomer, or an allyl monomer in the presence of the polymerization catalyst.

The (meth)acrylic acid ester monomer in the present invention is represented by the general formula: CH ₂ ═C(R ²¹ )CO ₂ (R ²² ). Here, R ²¹ is a hydrogen atom or a methyl group. R ²² is a hydrocarbon group having 1 to 30 carbon atoms, which may have a branch, a ring, and/or an unsaturated bond. Furthermore, R ²² may contain a heteroatom at any position.
If the carbon number of R ²² exceeds 30, the polymerization activity tends to decrease. Therefore, the carbon number of R ²² is 1 to 30, but R ²² preferably has 1 to 12 carbon atoms, and more preferably has 1 to 8 carbon atoms.
Examples of heteroatoms that may be included in R ²² include oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, and boron. Among these heteroatoms, oxygen, silicon, and fluorine are preferred, and oxygen is more preferred. It is also preferred that R ²² does not include a heteroatom.

More preferred (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. , hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene oxide (meth)acrylate, trifluoromethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. A single (meth)acrylic ester may be used, or multiple (meth)acrylic esters may be used in combination.

The vinyl monomer in the present invention is a vinyl monomer having a polar group such as a halogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and in particular a vinyl monomer containing a halogen atom, a hydroxyl group, an amino group, a nitro group, a carboxy group, a formyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an epoxy group, a nitrile group, or an imide group. Specifically, 5-hexen-1-ol, 2-methyl-3-buten-1-ol, ethyl 10-undecenoate, 10-undecen-1-ol, 12-tridecen-2-ol, 10-undecanoic acid, methyl-9-decenate, t-butyl-10-undecenate, 1,1-dimethyl-2-propen-1-ol, 9-decen-1-ol, 3-butenoic acid, 3-buten-1-ol, N-(3-buten-1-yl)phthalimide, 5-hexenoic acid, methyl 5-hexenoate, 5-hexen-2-one, acrylonitrile, methacrylonitrile, vinyl acetate, etc. are mentioned. Among these, 3-buten-1-ol, ethyl 10-undecenoate, and 10-undecen-1-ol are particularly preferable.

The allyl monomer in the present invention is exemplified by an allyl monomer having 3 carbon atoms (propenyl monomer) and an allyl-based monomer having 4 or more carbon atoms and an allyl group. The allyl monomer is an allyl monomer having a polar group containing a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc., and is particularly an allyl monomer containing a halogen atom, a hydroxyl group, an amino group, a nitro group, a carboxy group, a formyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an epoxy group, a nitrile group, an imide group, etc. Preferred specific examples include allyl acetate, allyl alcohol, allylamine, N-allylaniline, N-t-butoxycarbonyl-N-allylamine, N-benzyloxycarbonyl-N-allylamine, N-allyl-N-benzylamine, allyl chloride, allyl bromide, allyl ether, diallyl ether, etc. Among these, allyl acetate and allyl alcohol are particularly preferred, and allyl acetate, allyl ether, and diallyl ether are more preferred.

The polymerization reaction of the present invention is carried out in the presence or absence of a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, or a liquid such as a liquefied α-olefin, or a polar solvent such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, or the like. A mixture of the liquid compounds described herein may also be used as the solvent. Furthermore, an ionic liquid may also be used as the solvent. In order to obtain high polymerization activity and a high molecular weight, the above-mentioned hydrocarbon solvents and ionic liquids are more preferable.

In the present invention, the polymerization reaction can be carried out in the presence or absence of known additives. As the additive, a polymerization inhibitor that inhibits radical polymerization or an additive that has the effect of stabilizing the resulting copolymer is preferable. For example, quinone derivatives and hindered phenol derivatives are examples of preferable additives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of an alkoxide of tetravalent titanium and BHT, etc. can be used. In addition, inorganic and/or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers. Furthermore, ^L1 and ionic liquids according to the present invention may be used as additives.

A preferred additive in the present invention is a Lewis base. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylic acid ester can be improved. The amount of the Lewis base is 0.0001 equivalent to 1000 equivalents, preferably 0.1 equivalent to 100 equivalents, and more preferably 0.3 equivalent to 30 equivalents, relative to the transition metal M in the catalyst component present in the polymerization system. There is no particular limitation on the method of adding the Lewis base to the polymerization system, and any method can be used. For example, the Lewis base may be added by mixing with the catalyst component of the present invention, may be added by mixing with the monomer, or may be added to the polymerization system independently of the catalyst component and the monomer. In addition, a plurality of Lewis bases may be used in combination. In addition, the same Lewis base as L ¹ according to the present invention may be used, or may be different.

Examples of Lewis bases include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons. Of these, aromatic amines are particularly preferred Lewis bases.

Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo-[5.4.0]-undecane, Examples include carbo-7-ene, 1,4-diazabicyclo-[2,2,2]-octane, benzonitrile, picoline, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenyl phosphite, triphenyl phosphate, tripyrrolidinophosphine, and tris(pyrrolidino)borane.

In the present invention, there is no particular restriction on the polymerization type. Slurry polymerization in which at least a part of the polymer produced becomes a slurry in a medium, bulk polymerization in which the liquefied monomer itself is the medium, gas phase polymerization in a vaporized monomer, or high pressure ionic polymerization in which at least a part of the polymer produced is dissolved in a monomer liquefied at high temperature and high pressure are preferably used. In addition, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used. In addition, living polymerization may be used, or polymerization may be performed while chain transfer occurs. Furthermore, so-called chain transfer agent (CSA) may be used in combination to perform chain shuttling or coordinate chain transfer polymerization (CCTP).

The unreacted monomers and the medium may be separated from the resulting copolymer and recycled.
In recycling, these monomers and media may be purified before reuse, or may be reused without purification. A conventional method can be used to separate the resulting copolymer from the unreacted monomers and media. For example, filtration, centrifugation, solvent extraction, reprecipitation using a poor solvent, etc. can be used.
The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, but can usually be optimally set within the following ranges, taking into consideration productivity and process capacity: The polymerization temperature can usually be selected from the ranges of -20°C to 290°C, preferably 0°C to 250°C, the copolymerization pressure from 0.1 MPa to 300 MPa, preferably 0.3 MPa to 250 MPa, and the polymerization time from the ranges of 0.1 minute to 10 hours, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

In the present invention, the polymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen, argon or carbon dioxide atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed in.
There is no particular restriction on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, a method can be used in which a predetermined amount of monomer is supplied to the polymerization reactor in advance and a catalyst is supplied thereto. In this case, additional monomer or additional catalyst may be supplied to the polymerization reactor. In addition, in the case of continuous polymerization, a method can be used in which a predetermined amount of monomer and catalyst are supplied to the polymerization reactor continuously or intermittently to perform the polymerization reaction continuously.

Regarding the control of the copolymer composition, a method of controlling by supplying a plurality of monomers to a reactor and changing the supply ratio can be generally used. Other methods include a method of controlling the copolymer composition by utilizing the difference in monomer reactivity ratio due to the difference in catalyst structure, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependency of the monomer reactivity ratio.
When it is necessary to control the molecular weight of the polymer, a conventionally known method can be used. That is, a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, a method of controlling the molecular weight by using a chain transfer agent, a method of controlling the molecular weight by controlling the ligand structure in a transition metal complex, etc. can be mentioned. When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

In particular, the copolymer with the polar group-containing monomer obtained by the present invention exhibits good paintability, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibility with other resins due to the effects based on the polar groups of the copolymer. Taking advantage of these properties, the copolymer of the present invention can be used in a variety of applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizer, wax, etc.

The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto.
In the following synthesis examples, unless otherwise specified, operations were carried out under a purified nitrogen atmosphere, and solvents that had been dehydrated and deoxygenated were used.
In addition, the abbreviations used in the description are as follows.
BHT: 2,6-di-t-butyl 4-methylphenol DCM: dichloromethane AOc: acetyl MOM: methoxymethyl group (-CH ₂ OCH ₃ )
EtOAc: ethyl acetate, THF: tetrahydrofuran,
DMF: Dimethylformamide dba: Dibenzylideneacetone Tf: Trifluoromethanesulfonate s-Phos: 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

1. Evaluation Method (1) Weight Average Molecular Weight Mw, Number Average Molecular Weight Mn and Molecular Weight Distribution Mw/Mn
The weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw/Mn of the polymer were determined by the following GPC measurement.
A sample (about 20 mg) was collected in a vial for Polymer Laboratory's high-temperature GPC pretreatment device PL-SP 260VS, and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g/L) was added to adjust the polymer concentration to 0.1 (wt%). The polymer was dissolved by heating to 135°C in the high-temperature GPC pretreatment device PL-SP 260VS, and filtered through a glass filter to prepare a measurement sample. In the GPC measurement of the present invention, no polymer was captured by the glass filter. Next, GPC measurement was performed using Tosoh's TSKgel GMH6-HT (30 cm x 4 columns) as a column and Tosoh's HLC-8321GPC/HT equipped with an RI detector. The measurement conditions were as follows: sample solution injection amount: about 300 μL, column temperature: 135°C, solvent: o-dichlorobenzene, flow rate: 1.0 mL/min. The molecular weight was calculated as follows. That is, a commercially available monodisperse polystyrene was used as a standard sample, and a calibration curve relating to retention time and molecular weight was created from the viscosity equation of the polystyrene standard sample and the propylene-based polymer, and the molecular weight was calculated based on the calibration curve. Note that the viscosity equation used was [η]=K×Mα, where K=1.38E-4 and α=0.70 were used for polystyrene, and K=1.03E-4 and α=0.78 were used for the propylene-based polymer.

(2) Comonomer content in the copolymer
The stereoselectivity of the polymer was measured using a ¹ H-NMR measurement device (AVANCE500 manufactured by Bruker) according to the following procedure.
35 mg of the polymer was dissolved in o-dichlorobenzene- _d4 solvent, and the measurement was carried out under the conditions of 32 cumulative measurements and a measurement temperature of 60° C. The comonomer content was calculated from the integral ratio of the chemical shifts of ¹ H-NMR.

(3) Structure Assignment by NMR The structure of the ligand was assigned using an NMR measurement device (Bruker's "Ascend 400") according to the following procedure.
The ligand was dissolved in a deuterated solvent, and the measurement was carried out at 25° C. for 16 cumulative measurements.

2. Synthesis of Ligand (Synthesis Example 1): Synthesis of Ligand A Ligand A was synthesized according to the following scheme.

(i) Synthesis of Compound 2 Compound 2 was synthesized according to Japanese Patent No. 6913051.
(ii) Synthesis of Compound 4 Compound 4 was synthesized according to Japanese Patent No. 6913051.
(iii) Synthesis of Compound 5 To a solution of Compound 4 (6.31 g, 21.1 mmol) in THF (40 ml), nBuLi (2.5 M, 9.30 ml) was added dropwise at 0° C., the mixture was heated to 30° C., and then stirred for 2 hours. CuCl (2.30 g, 23.3 mmol) was added to this suspension at 0° C., the mixture was heated to 30° C., and then stirred for 1 hour. The reaction solution was cooled to −78° C., and tBu ₂ PCl (3.82 g, 21.1 mmol) was slowly added, and the mixture was stirred at 66° C. for 12 hours to obtain a blue suspension. The solvent was further removed under reduced pressure, and the mixture was purified using a silica gel column to obtain a pink solid.
To this pink solid, 80 ml of DCM and 100 ml of aqueous ammonia were added, and the mixture was stirred at 30° C. for 1 hour. The organic layer obtained after the separation operation was concentrated to obtain a crude product. This was purified using a silica gel column (developing solvent: petroleum ether (PE): ethyl acetate (EtOAc): DCM = 50: 1: 1) to obtain 2.40 g of compound 5.
(iv) Synthesis of Ligand A A solution of hydrochloric acid/EtOAc (4M, 80ml) was added to a solution of compound 5 (2.65g, 5.99mmol) in DCM (10ml) at 0°C, and the mixture was stirred at 30°C for 3 hours to obtain a colorless, transparent solution. After the solvent was removed under reduced pressure, the mixture was dissolved again in DCM (100ml), and the solution was washed with a saturated aqueous _NaHCO3 solution (100ml). The organic layer obtained after the liquid separation operation was concentrated to obtain 2.10g of Ligand A.
^1H NMR (400 MHz, _CDCl3 , δ, ppm): 1.09 (dd, 12H), 1.23 (s, 18H), 2.62 (m, 2H), 6.93 (t, 1H), 7.07 (dd, 1H), 7.22 (d, 2H), 7.35 (t, 1H), 7.60 (m, 1H), 7.83 (dd, 1H).
³¹ P NMR (162 MHz, CDCl ₃ , δ, ppm): −5.48 (s).

Synthesis Example 2: Synthesis of Ligand B Ligand B was synthesized according to the following scheme.

(i) Synthesis of Compound 8 Compound 6 (9.00 g, 52.9 mmol), compound 7 (37.1 g, 159 mmol), Pd(OAc) ₂ (469 mg, 2.64 mmol), and CsCO ₃ (68.9 g, 211 mmol) were dissolved in DMF (200 ml) and stirred at 100° C. for 44 hours to obtain a blue suspension solution. The solution was concentrated, and the remaining components were dissolved in EtOAc (800 ml) and filtered. The filtrate was washed three times with a saturated aqueous NH ₄ Cl solution (100 ml), and the organic layer obtained after the liquid separation operation was dried over Na ₂ SO _4. After filtration, the filtrate was concentrated to obtain a crude product as a black oily substance. The product was purified by performing a silica gel column (developing solvent: PE: EtOAc = 10: 1) twice, and 6.00 g of compound 8 was obtained as a pale yellow solid.
(ii) Synthesis of Compound 9 To a solution of compound 8 (10.0 g, 26.2 mmol) in THF (250 ml), NaH (2.61 g, 65.4 mmol) was added at 0° C., and the mixture was stirred at 0° C. for 1 hour. Subsequently, (methoxy)methane chloride (MOMCl, 8.42 g, 105 mmol) was added at 0° C., and the mixture was stirred at 25° C. for 12 hours to obtain a pale yellow suspension. The reaction was stopped by adding a saturated aqueous NaHCO ₃ solution (200 ml), and the product was extracted three times using EtOAc (200 ml). The organic layer obtained after the liquid separation operation was washed with saturated saline (100 ml). The organic layer obtained after the liquid separation operation was dried over Na ₂ SO _4. After filtration, the filtrate was concentrated to obtain a crude product. Washing was performed with PE (40 ml), and 8.80 g of compound 9 was obtained as a pale yellow solid.
(iii) Synthesis of Compound 10 To a solution of compound 9 (8.80 g, 20.6 mmol) in THF (50 ml), nBuLi (2.5 M, 10.3 ml) was added at 0° C., and the mixture was stirred at 25° C. for 2 hours. To the reaction solution, a solution of iodine (6.28 g, 24.8 mmol) in THF (20 ml) was slowly added at 0° C., and the mixture was stirred at 25° C. for 18 hours. Water (100 ml) was added to the resulting yellow reaction solution, and the product was extracted three times using EtOAc (100 ml). The organic layer obtained after the separation operation was washed twice with saturated Na ₂ S ₂ O ₃ (100 ml). The organic layer obtained after the separation operation was dried over Na ₂ SO _4. After filtration, the filtrate was concentrated to obtain a crude product as a white solid. Further purification was carried out using a silica gel column (developing solvent: PE: EtOAc = 10:1) to obtain 4.40 g of compound 10 as a white solid.

(iv) Synthesis of Compound 11 LiAlH ₄ (2.21 g, 58.1 mmol) was slowly added to a diethyl ether (70 ml) solution of tBu ₂ PCl (10.0 g, 55.4 mmol) at 0° C., and the mixture was stirred at 25° C. for 16 hours. The reaction was stopped by adding water (10 ml) to the white suspension. Further purification was performed by distillation under reduced pressure, and 8.00 g of Compound 11 was obtained as a transparent oily substance.

(v) Synthesis of Compound 12 Compound 10 (3.40 g, 6.15 mmol), compound 11 (0.90 g, 6.2 mmol), Pd ₂ (dba) 3 (0.56 g, 0.62 mmol), bis[2-(diphenylphosphino)phenyl]ether (DPEphos, 0.66 mg, 1.2 mmol), and sodium-tert-butoxide (1.18 g, 12.3 mmol) in toluene (100 ml) were stirred at 110° C. for 15 hours to obtain a black suspension solution. The solvent was distilled off under reduced pressure to obtain a crude product as a black oily substance. Furthermore, purification was performed using a silica gel column (developing solvent: PE: EtOAc: DCM = 98: 1: 1) to obtain 2.42 g of compound 12 as a colorless, transparent oily substance.

(vi) Synthesis of Compound 13 Dimethylsulfide borane (BH ₃ -Me ₂ S, 1.27 ml) was added dropwise to a solution of compound 12 (2.41 g, 4.22 mmol) in THF (20 ml) at 0° C., and the mixture was stirred at 25° C. for 16 hours to obtain a black suspension solution. Water (200 ml) was added to the reaction solution, and the product was extracted three times using EtOAc (200 ml). The organic layer obtained after the liquid separation operation was dried over Na ₂ SO _4. After filtration, the filtrate was concentrated to obtain a crude product as a yellow oily substance. Furthermore, 1.10 g of compound 13 was obtained as a white solid by HPLC purification.

(vii) Synthesis of Ligand B To a solution of compound 13 (1.40 g, 2.40 mmol) in DCM (3 ml), a solution of hydrochloric acid/EtOAc (4 M, 100 ml) was added and stirred at 25° C. for 3 hours. After the reaction solution was distilled off under reduced pressure, the remaining components were neutralized by adding a saturated aqueous NaHCO ₃ solution, and then the product was extracted three times using DCM (100 ml). The organic layer obtained after the liquid separation operation was concentrated to obtain 1.10 g of Ligand B as a white solid.
^1H NMR (400MHz, _CDCl3 , δ, ppm): 1.08 (d, 18H), 3.71 (s, 6H), 6.56 (t, 1H), 6.62 (m, 4H), 6.76 (dd, 1H), 7.08 (m, 4H), 7.28 (m, 1H), 7.38, (dd, 2H), 7.44 (dd, 1H), 7.72 (d, 1H).
³¹ P NMR (162 MHz, CDCl ₃ , δ, ppm): −6.85 (s).

Synthesis Example 3: Synthesis of Ligand C Ligand C was synthesized according to the following scheme.

(i) Synthesis of Compound 16 Compound 14 (20.0 g, 107 mmol), compound 15 (17.0 g, 139 mmol), Pd(PPh) ₄ (6.18 g, 5.35 mmol), and K ₂ CO ₃ (26.6 g, 193 mmol) were dissolved in toluene (100 ml) and stirred at 90° C. for 16 hours to obtain a yellow suspension solution. After filtering the reaction solution, the filtrate was washed three times with EtOAc (150 ml). The filtrate and the collected washings were concentrated to obtain a crude product as a black oily substance. Purification was performed using a silica gel column (PE:DCM=100:1 as the developing solvent), and 6.50 g of compound 16 was obtained as a pale yellow oily substance.

(ii) Synthesis of Compound 17 DCM (50 ml) was slowly added to compound 16 (2.20 g, 11.9 mmol) and triethylamine (5.08 g, 50.2 mmol) at 0° C., and the mixture was stirred for 30 minutes at 0° C. Then, Tf ₂ O (4.72 g, 16.7 mmol) was added at 0° C., and the mixture was stirred at 20° C. for 17 hours to obtain a brown suspension solution.
The reaction solution was diluted with methyl tert-butyl ether (MTBE, 150 ml), and dilute hydrochloric acid (1M, 150 ml) was added to stop the reaction. The organic layer was then washed with water (150 ml), and the product was extracted from the aqueous layer three times using EtOAc (150 ml). The organic layer obtained after the separation operation was washed with saturated saline (150 ml). The organic layer obtained after the separation operation was dried over Na ₂ SO _4. After filtration, the filtrate was concentrated to obtain a crude product. Purification was performed using a silica gel column (PE as a developing solvent), and 1.50 g of compound 17 was obtained as a yellow oily substance.

(iii) Synthesis of Compound 18 Compound 17 (1.00 g, 3.16 mmol), compound 2 (1.15 g, 6.32 mmol), K ₃ PO ₄ (1.01 g, 4.74 mmol) were added to a dioxane (10 ml) solution of compound 17 (1.00 g, 3.16 mmol), compound 2 (1.15 g, 6.32 mmol), and K 3 PO 4 (1.01 g, 4.74 mmol), and a brown suspension was obtained by adding Pd(PPh ₃ ) ₄ (0.18 g, 0.16 mmol) and stirring at 100° C. for 48 hours. After filtering the reaction solution, the residue was washed three times with EtOAc (10 ml). The filtrate and the collected washings were concentrated to obtain a crude product as a black oily substance. Further purification was performed using a silica gel column (PE: EtOAc = 20: 1 as the developing solvent), and 0.50 g of compound 18 was obtained as a colorless and transparent oily substance.

(iv) Synthesis of Compound 19 To a solution of compound 18 (1.75 g, 5.75 mmol) in THF (10 ml), nBuLi (2.5 M, 2.53 ml) was added dropwise at 0° C., and the mixture was stirred at 20° C. for 1.5 hours. Iodine (1.75 g, 6.90 mmol) was added to the reaction solution at 0° C., and the mixture was stirred at 20° C. for 16 hours to obtain a yellow suspension solution. The reaction was stopped by adding a saturated aqueous Na ₂ S ₂ O ₃ solution (30 ml), and the product was extracted three times using EtOAc (30 ml). The organic layer obtained after the liquid separation operation was dried over Na ₂ SO ₄ , filtered, and the filtrate was concentrated to obtain 2.40 g of crude compound 19 as a yellow oily substance. Compound 19 was not further purified and was used in the next reaction.

(v) Synthesis of Compound 20 A solution of compound 19 (2.40 g, 5.58 mmol), compound 11 (0.82 g, 5.6 mmol), sodium tert-butoxide (1.07 g, 11.2 mmol) and Pd(PPh ₃ ) ₄ (0.51 g, 560 μmol) in toluene (15 ml) was stirred at 110° C. for 16 hours. BH ₃ -Me ₂ S (10 M, 2.8 mL) was added at 0° C., and the mixture was stirred at 20° C. for 16 hours to obtain a brown suspension. Water (150 ml) was added to the reaction solution, and the product was extracted three times using EtOAc (150 ml). The organic layer obtained after the liquid separation operation was dried over Na ₃ SO ₄ , filtered, and concentrated to obtain a crude product as a dark yellow oily substance. Purification was carried out using a silica gel column (developing solvent: PE: EtOAc: DCM = 100: 1: 1) and HPLC to obtain 0.8 g of compound 20 as a white solid.

(vi) Synthesis of Ligand C A solution of hydrochloric acid/EtOAc (4M, 80 ml) was added to a solution of compound 20 (3.00 g, 6.49 mmol) in DCM (3 ml) at 0° C., and the mixture was stirred at 20° C. for 5 hours to obtain a colorless, transparent solution. After concentration, a saturated aqueous NaHCO ₃ solution (100 ml) was added for neutralization, and the product was extracted three times using DCM (150 ml). The organic layer obtained after the liquid separation operation was concentrated to obtain 2.50 g of Ligand C as a white solid.
^1H NMR (400MHz, _CDCl3 , δ, ppm): 1.19 (q, 18H), 2.15 (s, 3H), 6.86 (t, 1H), 6.81 (dd, 1H), 7.06 (m, 3H), 7.15 (m, 2H), 7.25-7.34 (m, 3H), 7.42 (m, 1H), 7.98 (d, 1H).
^31P NMR (162MHz, _CDCl3 , δ, ppm): -6.52.

(Comparative Synthesis Example 1): Synthesis of Ligand B-349 According to Synthesis Example 2-1 of WO 2018/021446, ligand B-349 having the following structure was synthesized.

(Comparative Synthesis Example 2): Synthesis of Ligand B-396 According to Synthesis Example 2-3 of WO 2018/021446, ligand B-396 having the following structure was synthesized.

(Comparative Synthesis Example 3): Synthesis of Ligand B-394 According to Synthesis Example 3-1 of WO 2018/021446, ligand B-394 having the following structure was synthesized.

(Comparative Synthesis Example 4): Synthesis of Ligand B-400 According to Synthesis Example 3-2 of WO 2018/021446, ligand B-400 having the following structure was synthesized.

3. Polymerization evaluation (Example 1): Homopolymerization of propylene using ligand A (1) Synthesis of metal complex All of the following operations were carried out under a nitrogen atmosphere. Hereinafter, bis-1.5-cyclooctadiene nickel (0) will be referred to as Ni(COD) ₂ .
Ni(COD) ₂ (70.0 mg, 0.254 mmol) was weighed into a two-necked eggplant flask, and toluene (12.85 mL) was added to make a 0.02 mmol/mL solution. 11.6 mL of this toluene solution of Ni(COD) ₂ was added to the two-necked eggplant flask containing Ligand A (92.3 mg, 0.232 mmol) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 30 minutes.
The color of the reaction solution changed from yellow to orange. A 0.02 mmol/mL solution of the reaction product of ligand A and Ni(COD) ₂ ((A)Ni(σ,π-cyclooct-4-enyl)) was obtained. The concentration of the reaction product was calculated assuming that ligand A and Ni(COD) ₂ reacted in a 1:1 ratio to form a nickel complex.

(2) Homopolymerization of propylene Propylene (500 mL) was introduced into an induction stirring autoclave with an internal volume of 2 L. A 0.02 mmol/mL solution (5.0 mL) of the reaction product of ligand A and Ni(COD) ₂ obtained in (1) above was fed into the autoclave. The autoclave was heated to 50° C. while stirring the mixture to start polymerization. After polymerization for 1 hour, the remaining propylene was removed to stop the reaction. The autoclave was then opened to obtain a polymer. The polymerization results are shown in Table 3. The activity represents the polymer yield (g) per mol of the metal complex used in the polymerization. The results of GPC for the obtained polymer are also shown in Table 3. The activity was calculated assuming that ligand A and Ni(COD) ₂ reacted in a 1:1 ratio to form a nickel complex.

Example 2: Homopolymerization of propylene using ligand B (1) Synthesis of metal complex A metal complex was synthesized in the same manner as in Example 1, except that the ligand B obtained in Synthesis Example 2 was used as the ligand.
(2) Homopolymerization of Propylene Polymerization was carried out in the same manner as in Example 1, except that the solution of the reaction product obtained in (1) above was used.

Example 3: Homopolymerization of propylene using ligand C (1) Synthesis of metal complex A metal complex was synthesized in the same manner as in Example 1, except that the ligand C obtained in Synthesis Example 3 was used as the ligand.
(2) Homopolymerization of Propylene Polymerization was carried out in the same manner as in Example 1, except that the solution of the reaction product obtained in (1) above was used.

Comparative Example 1: Homopolymerization of propylene using ligand B-349 (1) Synthesis of comparative metal complex A metal complex was synthesized in the same manner as in Example 1, except that the ligand B-349 obtained in Comparative Synthesis Example 1 was used as the ligand.
(2) Homopolymerization of Propylene Polymerization was carried out in the same manner as in Example 1, except that the solution of the reaction product obtained in (1) above was used.

Comparative Example 2: Homopolymerization of propylene using ligand B-396 (1) Synthesis of comparative metal complex A metal complex was synthesized in the same manner as in Example 1, except that the ligand B-396 obtained in Comparative Synthesis Example 2 was used as the ligand.
(2) Homopolymerization of Propylene Polymerization was carried out in the same manner as in Example 1, except that the solution of the reaction product obtained in (1) above was used.

(Comparative Example 3): Homopolymerization of propylene using ligand B-394 (1) Synthesis of comparative metal complex A metal complex was synthesized in the same manner as in Example 1, except that the ligand B-394 obtained in Comparative Synthesis Example 3 was used as the ligand.

(2) Homopolymerization of Propylene Polymerization was carried out in the same manner as in Example 1, except that the solution of the reaction product obtained in (1) above was used.

Example 4: Copolymerization of propylene and ethyl 10-undecenoate using ligand A (1) Synthesis of metal complex A metal complex was synthesized in the same manner as in Example 1.
(2) Copolymerization of Propylene and Ethyl 10-Undecenoate Polymerization was carried out in the same manner as in Example 1, except that the reaction product obtained in (1) above was used, and further, ethyl 10-undecenoate (12 mL, 50 mmol) and tri-normal octyl acrylate (0.1 mmol) were used. The results are shown in Table 4.

Comparative Example 4: Copolymerization of propylene and ethyl 10-undecenoate using ligand B-400 (1) Synthesis of comparative metal complex A metal complex was synthesized in the same manner as in Example 1, except that ligand B-400 obtained in Comparative Synthesis Example 4 was used as the ligand.
(2) Copolymerization of Propylene and Ethyl 10-Undecenoate Polymerization was carried out in the same manner as in Example 1, except that the reaction product obtained in (1) above was used, and further, ethyl 10-undecenoate (12 mL, 50 mmol) and tri-normal octyl acrylate (0.1 mmol) were used. The results are shown in Table 4.

4. Discussion From the results of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 3, it was confirmed that the metal complex having the ligand specified in the present invention is an olefin polymerization catalyst that is highly active in propylene homopolymerization and gives a polymer with a higher molecular weight, as compared with a metal complex having a known phosphinophenolate ligand.
Furthermore, from the results of Example 4 and Comparative Example 4 shown in Table 4, it was confirmed that the metal complex having the ligand specified in the present invention is an olefin polymerization catalyst that is highly active and gives a high molecular weight copolymer even in the copolymerization of propylene and ethyl 10-undecenoate, as compared with a metal complex having a known phosphinophenolate ligand.

Claims (17)

A metal complex which is a reaction product between a compound represented by the following general formula [1] or [2] and a transition metal compound containing nickel or palladium:
[In formula [1] and formula [2],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
Z ¹ represents a hydrogen atom or a leaving group, and m represents the valence of Z ¹ . A metal complex represented by the following general formula [3]:
[In formula [3],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
M represents nickel or palladium.
^L1 represents a ligand coordinated to M.
^R13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. ^R13 and ^L1 may be bonded to each other to form a ring.] 3. The metal complex according to claim 1, wherein at least one of R ⁴ and R ⁸ is independently (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ). 3. The metal complex according to claim 1, wherein at least one of R ⁴ and R ⁸ is independently (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which optionally has at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. The metal complex according to claim 1 or 2, wherein ^E1 is a phosphorus atom. The metal complex according to claim 1 or 2, wherein X ¹ is an oxygen atom. The metal complex of claim 2, wherein M is nickel. A catalyst component for olefin polymerization comprising the metal complex according to claim 1. A catalyst component for olefin polymerization comprising the metal complex according to claim 2. An olefin polymerization catalyst comprising a reaction product of a compound represented by the following general formula [1] or [2] and a transition metal compound containing nickel or palladium:
[In formula [1] and formula [2],
R ¹ , R ² and R ³ each independently represent an atom or group selected from the group consisting of the following (i) to (iv):
(i) a hydrogen atom; (ii) a halogen atom; (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom; (iv) OR ¹¹ , CO ₂ R ¹¹ , CO ₂ M', C(O)N(R ¹² ) ₂ , C(O)R ¹¹ , OC(O)R ¹¹ , SR ¹¹ , SO ₂ R ¹¹ , OSO ₂ R ¹¹ , P(O)(OR ¹¹ ) _2-y (R ¹¹ ) _y , CN, NR ¹¹ (R ¹² ), Si(OR ¹² ) _3-x (R ¹² ) _x , OSi(OR ¹² ) _3-x (R ¹² ) _x , NO ₂ , SO ₃ M', PO ₃ M'. ₂ , P(O)(OR ¹² ) ₂ M', or an epoxy-containing group. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium, x represents an integer from 0 to 3, and y represents an integer from 0 to 2.
Adjacent substituents of R ¹ , R ² and R ³ may be linked together to form an alicyclic ring, an aromatic ring, or a heterocyclic ring containing a heteroatom. The ring has 5 to 8 members and may or may not have a substituent on the ring.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent (i) a hydrogen atom, (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom, or (vi) OR ¹¹ , SR ¹¹ or NR ¹¹ (R ¹² ), provided that at least one of R ⁴ to R ⁸ is other than a hydrogen atom.
R ⁹ and R ¹⁰ each independently represent a non-aromatic hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, NR ¹¹ (R ¹² ), or SiR ¹¹ (R ¹² ) ₂ .
^E1 represents phosphorus, arsenic, or antimony.
^X1 represents an oxygen atom or a sulfur atom.
Z ¹ represents a hydrogen atom or a leaving group, and m represents the valence of Z ¹ . The olefin polymerization catalyst according to claim 10, wherein at least one of R ⁴ and R ⁸ is each independently (v) an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, optionally having at least one selected from the group consisting of heteroatoms and groups containing heteroatoms, or (vi) OR ¹¹ , SR ¹¹ , or NR ¹¹ (R ¹² ). The olefin polymerization catalyst according to claim 10, wherein at least one of R ⁴ and R ⁸ is each independently (v) an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which optionally has at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. The olefin polymerization catalyst according to claim 10, wherein E ¹ is a phosphorus atom. The olefin polymerization catalyst according to claim 10, wherein X ¹ is an oxygen atom. An olefin polymerization catalyst comprising the olefin polymerization catalyst component according to claim 9. A method for producing an olefin polymer by polymerizing or copolymerizing an olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst according to any one of claims 10 to 15. The method for producing an olefin polymer according to claim 16, wherein the olefin is propylene.