Olefin polymerization catalyst and method for producing olefin polymer

Abstract

Provided are a catalyst and a method that enable the production of an olefin-based polymer, which has a polar group and is usable for various applications, at high catalytic activity. A metal complex shown in general formula (C1) (in the formula, M represents a palladium atom or a nickel atom, X represents a phosphorus atom (P), R5-R9 are as set forth in the claims, L represents an electron donating ligand, and q is 0, 1 / 2, 1, or 2) is used as a catalyst for polymerization of an olefin having a polar group.

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization, an olefin polymer, and a method for producing a polar group-containing monomer polymer such as an allyl compound having a polar group.

Background Art

[0002] Copolymers of olefins such as ethylene and propylene, which are non-polar monomers, and vinyl monomers having a polar group have functions and properties not possessed by non-polar polyethylene and polypropylene, and are used in a wide range of fields. In particular, ethylene-vinyl alcohol copolymer (EVOH) is a copolymer composed of ethylene monomer structural units and vinyl alcohol monomer structural units, and is produced by saponifying an ethylene-vinyl acetate copolymer obtained by radical copolymerization of ethylene and vinyl acetate. EVOH is used in a wide range of fields such as food packaging applications by taking advantage of its excellent gas barrier properties.

[0003] On the other hand, the polymerization of monomers having an allyl group is more difficult than that of ordinary vinyl monomers, and its polymers are hardly known. The main reason is that when a monomer having an allyl group is radical polymerized, due to the degenerative chain transfer reaction to the monomer by hydrogen atom abstraction existing on the allylic carbon, the growth reaction of the polymer is extremely slow, and only oligomers with a low degree of polymerization can be obtained (Chem. Rev. 58, 808 (1958); Non-Patent Document 1).

[0004] JP 2011-68881 A (US Patent No. 8916663; Patent Document 1), JP 2014-159540 A (US Patent No. 9499644; Patent Document 2), JP 2015-137282 A (Patent Document 3), WO 2019 / 093364 (Patent Document 4), WO 2020 / 175482 (Patent Document 5), and J. Am. Chem. Soc., 133, 1232 (2011) (Non-Patent Document 2) disclose the coordination copolymerization of ethylene and allyl monomers containing polar groups using Group 10 metal complex catalysts, and have succeeded in synthesizing allyl monomer copolymers containing polar groups that could not be obtained by radical polymerization methods. However, in conventional production methods, the catalytic activity is insufficient, and there are still problems for industrialization from the viewpoints of catalyst cost and the like.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0006]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a catalyst and a method capable of producing an olefin polymer having a polar group applicable to various applications with high catalytic activity. **Means for Solving the Problems**

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that by using a novel Group 10 metal complex of the periodic table as a catalyst and copolymerizing a vinyl monomer (non-polar olefin) such as ethylene or propylene alone or the non-polar olefin and an olefin containing a polar group (including an allyl monomer having a polar group), an olefin polymer having a polar group applicable to various applications can be produced with high catalytic activity, and thus the present invention has been completed.

[0009] That is, the present invention relates to an olefin polymerization catalyst of the following [1] to [5] and a method for producing a (co)polymer of ethylene of [6] to

[12] . [1] General formula (C1) [Chemical formula] (In the formula, M represents a palladium atom or a nickel atom, and X represents a phosphorus atom (P). R 5 represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R 6 and R 7 each independently represent a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group. R8 and R 9 each independently represents a hydrogen atom or a halogen atom. L represents an electron-donating ligand, and q is 0, 1 / 2, 1, or 2.) A catalyst for olefin polymerization containing a metal complex represented by [2] R in the general formula (C1) 8 and R 9 each independently is a hydrogen atom or a chlorine atom, the olefin polymerization catalyst according to [1]. [3] R in the general formula (C1) 8 and R 9 wherein one of them is a hydrogen atom and the other is a chlorine atom, the olefin polymerization catalyst according to [2]. [4] R in the general formula (C1) 8 and R 9 both are chlorine atoms, the olefin polymerization catalyst according to [2]. [5] R in the general formula (C1) 6 and R 7 each independently is an alkyl group, a fluoroalkyl group, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, the olefin polymerization catalyst according to any one of [1] to [4]. [6] R in the general formula (C1) 6 and R 7 both are an isopropyl group, a t-butyl group, a menthyl group, a 2,7-di-t-butyl-9-fluorenyl group, a diphenylmethyl group, a 2-methoxyphenyl group, or a 2-isopropylphenyl group, the olefin polymerization catalyst according to any one of [1] to [5]. [7] General formula (C1)

Chemical formula

Chemical formula

[10] R in the general formula (C1) 8 and R 9 are each independently a hydrogen atom or a chlorine atom, and the method according to any one of [7] to [9].

[11] R in the general formula (C1) 8 and R 9 wherein one of them is a hydrogen atom and the other is a chlorine atom, and the method according to

[10] .

[12] R in the general formula (C1) 8 and R 9 are both chlorine atoms, and the method according to

[10] .

[13] R in the general formula (C1) 6 and R 7Each independently is an alkyl group, a fluoroalkyl group, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, the method according to any one of [7] to

[12] .

[14] R in general formula (C1) 6 and R 7 both are an isopropyl group, a t-butyl group, a menthyl group, a 2,7-di-t-butyl-9-fluorenyl group, a diphenylmethyl group, a 2-methoxyphenyl group, or a 2-isopropylphenyl group, the method according to any one of [7] to

[13] . [Advantages of the Invention]

[0010] According to the present invention, there are provided a catalyst and a method capable of producing an olefin polymer having a polar group applicable to various applications with high catalytic activity. For example, by copolymerizing a non-polar olefin (ethylene) and an olefin having a polar group such as an allyl monomer having a polar group using the olefin polymerization catalyst of the present invention, an olefin polymer having a polar group applicable to various applications can be produced at low cost. [Embodiments for Carrying Out the Invention]

[0011] [Catalyst] The catalyst comprising a palladium metal complex or a nickel metal complex used in the present invention is represented by general formula (C1). [Chemical Formula]

[0012] In the formula, M represents a palladium atom or a nickel atom, and X represents a phosphorus atom (P). R 5represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R 6 and R 7 each independently represents a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group. R 8 and R 9 each independently represents a hydrogen atom or a halogen atom. L represents an electron-donating ligand, and q is 0, 1 / 2, 1, or 2.

[0013] In this specification, "hydrocarbon" includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons.

[0014] Hereinafter, the structure of the general formula (C1) will be described.

[0015] M represents a palladium atom (Pd) or a nickel atom (Ni). From the viewpoints of catalytic activity and the molecular weight of the resulting polymer, a palladium atom (Pd) is more preferable.

[0016] X is a phosphorus atom (P) and is coordinated to the central metal M with two electrons.

[0017] R 5represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms.

[0018] R 5 Preferable specific examples of the halogen atom represented by 5 R include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a chlorine atom is preferable.

[0019] R 5The hydrocarbon group having 1 to 30 carbon atoms represented by is preferably a hydrocarbon group having 1 to 13 carbon atoms. As the hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group are preferable, and an alkyl group and an aralkyl group are more preferable. Preferable specific examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, benzyl group, and p-ethylphenyl group. Among these, a methyl group and a benzyl group are more preferable, and a methyl group is particularly preferable.

[0020] R 5 The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with fluorine, chlorine, or bromine, and preferable specific examples include a trifluoromethyl group and a pentafluorophenyl group.

[0021] R 5The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, or a t-butoxy group. More preferably, it is a hydrocarbon group having 2 to 6 carbon atoms substituted with a methoxy group or an ethoxy group. Specific examples include a 1-(methoxymethyl)ethyl group, a 1-(ethoxymethyl)ethyl group, a 1-(phenoxymethyl)ethyl group, a 1-(methoxyethyl)ethyl group, a 1-(ethoxyethyl)ethyl group, a di(methoxymethyl)methyl group, a di(ethoxymethyl)methyl group, and a di(phenoxymethyl)methyl group. Particularly preferred are a 1-(methoxymethyl)ethyl group and a 1-(ethoxymethyl)ethyl group.

[0022] R 5 The hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, or a 2,6-di-t-butylphenoxy group. More preferably, it is a hydrocarbon group having 1 to 6 carbon atoms substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferably, it is a 1-(phenoxymethyl)ethyl group and a 1-(2,6-dimethylphenoxymethyl)ethyl group.

[0023] R 5 The hydrocarbon group having 3 to 30 carbon atoms substituted with an amido group having 2 to 10 carbon atoms (R-(C=O)NH-, R is an organic group) represented by is preferably a substituent obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with an acetamido group, a propionylamino group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, or a benzoylamino group. More preferably, they are a 2-acetamidophenyl group, a 2-propionylaminophenyl group, a 2-valerylaminophenyl group, and a 2-benzoylaminophenyl group, and particularly preferably, it is a 2-acetamidophenyl group.

[0024] R 5 The alkoxy group having 1 to 30 carbon atoms represented by R is preferably an alkoxy group having 1 to 6 carbon atoms. Preferred specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a t-butoxy group. Among these, more preferably, a methoxy group, an ethoxy group, and an isopropoxy group, and particularly preferably a methoxy group.

[0025] R 5 The aryloxy group having 6 to 30 carbon atoms represented by R is preferably an aryloxy group having 6 to 12 carbon atoms. Preferred specific examples include a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, and a 2,6-di-t-butylphenoxy group. Among these, more preferably a phenoxy group and a 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group.

[0026] R 5 The acyloxy group having 2 to 10 carbon atoms represented by R is preferably an acyloxy group having 2 to 8 carbon atoms. Preferred specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, and a benzoyloxy group. Among these, more preferably an acetyloxy group, a propionyloxy group, and a benzoyloxy group, and particularly preferably an acetyloxy group and a propionyloxy group.

[0027] These Rs 5Among the preferred groups, more preferably, they are a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms, and most preferably, a hydrocarbon group having 1 to 30 carbon atoms. Particularly preferred specific examples include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group, and an acetyloxy group.

[0028] R 6 and R 7 each independently represents a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group.

[0029] R 6 and R 7 As the alkoxy group represented by R and R, those having 1 to 20 carbon atoms are preferred, and examples include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0030] R 6 and R 7 As the aryloxy group represented by R and R, those having 6 to 24 carbon atoms are preferred, and an example is a phenoxy group.

[0031] R 6 and R 7 Examples of the silyl group represented by R and R include a trimethylsilyl group. Examples of the amino group include an amino group, a methylamino group, and a dimethylamino group.

[0032] R 6 and R 7The halogen atom in the hydrocarbon group having 1 to 180 carbon atoms, which may be substituted with one or more groups selected from a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group represented by, is a fluorine atom, a chlorine atom, or a bromine atom, and a fluorine atom is preferred. The alkoxy group preferably has 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The aryloxy group preferably has 6 to 24 carbon atoms, and an example thereof is a phenoxy group. Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a benzoyloxy group. The number of carbon atoms of the hydrocarbon group having 1 to 180 carbon atoms includes the number of carbon atoms of the aforementioned substituents.

[0033] R 6 and R 7Specific examples of the hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group and an acyloxy group represented by include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-methyl-4-heptyl group, 2,6-dimethyl-4-heptyl group, 3-methyl-4-heptyl group; fluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, menthyl group, 1-adamantyl group, 2-adamantyl group; aralkyl groups such as benzyl group, 2'-methoxybenzyl group, 3'-methoxybenzyl group, 4'-methoxybenzyl group, 4'-trifluoromethylbenzyl group, 9-fluorenyl group, 2,7-di-t-butyl-9-fluorenyl group, diphenylmethyl group; and aryl groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl group, 2',6'-dimethoxy-2-biphenyl group, 2'-methyl-2-biphenyl group, 2',4',6'-triisopropyl-2-biphenyl group.

[0034] R 6 and R 7 may be the same or different.

[0035] Furthermore, R 6 and R 7 are each independently preferably an alkyl group, a fluoroalkyl group, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, from the viewpoints of ease of synthesis and catalytic activity. The substituent is preferably an alkoxy group having 1 to 6 carbon atoms. More specifically, R 6 and R 7 are each independently preferably an isopropyl group, a cyclohexyl group, a t-butyl group, a menthyl group, a 9-fluorenyl group, a 2,7-di-t-butyl-9-fluorenyl group, a diphenylmethyl group, a 2-phenyl group, a 2-isopropylphenyl group, or a 2-methoxyphenyl group, and R 6 and R 7 are each particularly preferably an isopropyl group, a t-butyl group, a menthyl group, a 2,7-di-t-butyl-9-fluorenyl group, a diphenylmethyl group, a 2-methoxyphenyl group, or a 2-isopropylphenyl group.

[0036] R 8 and R 9 each independently represents a hydrogen atom or a halogen atom.

[0037] R 8 and R 9 Preferred specific examples of the halogen atom represented by are a fluorine atom, a chlorine atom, and a bromine atom. Among these, a chlorine atom is particularly preferred.

[0038] In one embodiment, R 8 and R 9 are each independently a hydrogen atom or a chlorine atom. It is preferable that one of R 8 and R 9 is a hydrogen atom and the other is a chlorine atom. R 8and R 9 It is also preferable that all of them are chlorine atoms.

[0039] The electron-donating ligand (L) is a compound having an electron-donating group and capable of coordinating to the metal atom M to stabilize the metal complex.

[0040] Examples of the electron-donating ligand (L) having a sulfur atom include dimethyl sulfoxide (DMSO). Examples of the electron-donating ligand (L) having a nitrogen atom include trialkylamines having 1 to 10 carbon atoms in the alkyl group, dialkylamines having 1 to 10 carbon atoms in the alkyl group, pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N,N,N’,N’-tetramethylethylenediamine (TMEDA), 4-(N,N-dimethylamino)pyridine (DMAP), acetonitrile, benzonitrile, quinoline, and 2-methylquinoline. Examples of the electron-donating ligand (L) having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoints of the stability and catalytic activity of the metal complex, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), and N,N,N’,N’-tetramethylethylenediamine (TMEDA) are preferable, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (also known as 2,6-lutidine) are more preferable.

[0041] q is 0, 1 / 2, 1, or 2. When q is 1 / 2, it means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1 / 2 or 1 in terms of stabilizing the metal complex catalyst. When q is 0, it means that there is no ligand.

[0042] The metal complex represented by the general formula (C1) can be synthesized by the method described in known literature (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a source of M in the 0-valent or 2-valent state with the ligand in the general formula (C1).

[0043] Examples of the zero-valent M source include tris(dibenzylideneacetone)dipalladium as a palladium source, and tetracarbonylnickel(0): Ni(CO)4 and bis(1,5-cyclooctadiene)nickel as nickel sources.

[0044] Examples of the divalent M source include (1,5-cyclooctadiene)(methyl)palladium chloride, palladium chloride, palladium acetate, bis(acetonitrile)dichloropalladium: PdCl2(CH3CN)2, bis(benzonitrile)dichloropalladium: PdCl2(PhCN)2, (N,N,N’,N’-tetramethylethylenediamine)dichloropalladium(II): PdCl2(TMEDA), (N,N,N’,N’-tetramethylethylenediamine)dimethylpalladium(II): PdMe2(TMEDA), bis(acetylacetonato)palladium(II): Pd(acac)2 (acac = acetylacetonato), and palladium(II) trifluoromethanesulfonate: Pd(OSO2CF3)2 as palladium sources, and (allyl)nickel chloride, (allyl)nickel bromide, nickel chloride, nickel acetate, bis(acetylacetonato)nickel(II): Ni(acac)2, (1,2-dimethoxyethane)dichloronickel(II): NiCl2(DME), and nickel(II) trifluoromethanesulfonate: Ni(OSO2CF3)2 as nickel sources.

[0045] The metal complex represented by the general formula (C1) can be used in isolated form, but it is also possible to bring the metal source containing M and the ligand precursor into contact in the reaction system without isolating the complex and use it directly (in situ) for polymerization. In particular, when R 5 in the general formula (C1) is a hydrogen atom, it is preferable to react the metal source containing zero-valent M with the ligand precursor and then use it directly for polymerization without isolating the complex.

[0046] In this case, the ligand precursor in the general formula (C1) is, for example, the following formula (C1-1) or (C1-2) in the case of the general formula (C1). [Chemical formula] (The symbols in the formula represent the same meanings as described above.) It is represented by

[0047] The ratio ((C1 ligand) / M) of the M source (M) to the ligand precursor (C1-1) or (C1-2) (C1 ligand) in the general formula (C1) is preferably selected from the range of 0.5 to 2.0, more preferably from the range of 1.0 to 1.5.

[0048] When isolating the metal complex of the general formula (C1), it is also possible to use one that is pre-coordinated with an electron-donating ligand (L) and stabilized. In this case, q is 1 / 2, 1, or 2. As described above, q being 1 / 2 means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1 / 2 or 1 in terms of stabilizing the metal complex catalyst. Note that when q is 0, it means that there is no ligand.

[0049] The metal complex represented by the general formula (C1) can also be supported on a carrier and used for polymerization. The carrier in this case is not particularly limited, and examples include inorganic carriers such as silica gel and alumina, and organic carriers such as polystyrene, polyethylene, and polypropylene. Examples of the method for supporting the metal complex include a physical adsorption method in which a solution of the metal complex is impregnated into the carrier and dried, and a method in which the metal complex and the carrier are chemically bonded and supported.

[0050] [Monomer] In the method for producing the polymer of the present invention, not only ethylene can be homopolymerized, but also ethylene can be copolymerized with an olefin having a polar group. The olefin having a polar group, which is the second monomer used for copolymerization in the present invention, has the general formula (1). [Chemical formula] It is represented by

[0051] In the formula, R 1 represents a substituent selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R-O-(C=O)-, where R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, a substituted amide group having 2 to 12 carbon atoms, a substituted pyridyl group having 5 to 10 carbon atoms, a substituted pyrrolidyl group having 4 to 10 carbon atoms, a substituted piperidyl group having 5 to 10 carbon atoms, a substituted hydrofuryl group having 4 to 10 carbon atoms, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. n is an integer selected from 0 to 6.

[0052] R being an alkoxy group having 1 to 10 carbon atoms 1 is preferably an alkoxy group having 1 to 4 carbon atoms, and preferred specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a t-butoxy group. Among these, more preferably are a methoxy group, an ethoxy group, and an isopropoxy group, and particularly preferably a methoxy group.

[0053] R being an aryloxy group having 6 to 20 carbon atoms 1 is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples include a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, a 3,5-di-t-butylphenoxy group, and a 2,6-di-t-butylphenoxy group. Among these, more preferably are a phenoxy group, a 3,5-di-t-butylphenoxy group, and a 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group and a 3,5-di-t-butylphenoxy group.

[0054] R being an acyl group having 2 to 10 carbon atoms 1is preferably an acyl group having 2 to 8 carbon atoms. Preferred specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, and a benzoyl group. Among these, an acetyl group, a pivaloyl group, and a benzoyl group are more preferable, and a benzoyl group is particularly preferable.

[0055] In an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R-O-(C=O)-, where R is an organic group), the organic group R is preferably an alkyl group which may have a functional group such as a hydroxyl group or an epoxy group, or an aryl group which may have the functional group. 1 is preferably an ester group having 2 to 8 carbon atoms. Preferred specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a (4-hydroxybutoxy)carbonyl group, a (4-glycidylbutoxy)carbonyl group, and a phenoxycarbonyl group. Among these, a methoxycarbonyl group, an ethoxycarbonyl group, and a (4-hydroxybutoxy)carbonyl group are more preferable, and a methoxycarbonyl group is particularly preferable.

[0056] R is an acyloxy group having 2 to 10 carbon atoms 1 is preferably an acyloxy group having 2 to 8 carbon atoms. Preferred specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, and a benzoyloxy group. Among these, an acetyloxy group, a propionyloxy group, and a benzoyloxy group are more preferable, and an acetyloxy group and a propionyloxy group are particularly preferable.

[0057] R is a substituted amino group having 1 to 12 carbon atoms 1Preferable specific examples include a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, a monophenylamino group, a diphenylamino group, a bis(trimethylsilyl)amino group, and a morpholinyl group. Among these, a dimethylamino group and a diphenylamino group are more preferable.

[0058] In a substituted amide group having 1 to 12 carbon atoms (R-(C=O)NH-, where R is an organic group), the organic group R is preferably an alkyl group which may have a functional group such as a hydroxyl group or an epoxy group, or an aryl group which may have the functional group. R 1 Preferable specific examples include an acetamide group, a propionylamino group, a butyrylamino group, an isobutyrylamino group, a valeryl amino group, an isovaleryl amino group, a pivaloyl amino group, and a benzoyl amino group. Among these, an acetamide group, a propionylamino group, and a benzoyl amino group are more preferable, and an acetamide group is particularly preferable.

[0059] R which is a substituted pyridyl group having 5 to 10 carbon atoms 1 Preferable specific examples include a 2-pyridyl group, a 3-pyridyl group, a 2-(3-methyl)pyridyl group, a 2-(4-methyl)pyridyl group, a 3-(2-methyl)pyridyl group, a 3-(4-methyl)pyridyl group, a 2-(4-chloromethyl)pyridyl group, and a 3-(4-chloromethyl)pyridyl group. Among these, a 2-pyridyl group, a 3-pyridyl group, and a 2-(4-methyl)pyridyl group are more preferable, and a 2-pyridyl group is particularly preferable.

[0060] R which is a substituted pyrrolidyl group having 4 to 10 carbon atoms 1Preferable specific examples thereof include a 2-pyrrolidyl group, 3-pyrrolidyl group, 2-(1-methyl)pyrrolidyl group, 2-(1-butyl)pyrrolidyl group, 2-(1-cyclopentenyl)pyrrolidyl group, 2-(4-methoxycarbonyl)pyrrolidyl group, 2-(5-methoxycarbonyl)pyrrolidyl group, and 2-(6-methoxycarbonyl)pyrrolidyl group. Among these, more preferable are a 2-pyrrolidyl group, 3-pyrrolidyl group, 2-(1-methyl)pyrrolidyl group, and 2-(6-methoxycarbonyl)pyrrolidyl group, and particularly preferable is a 2-pyrrolidyl group.

[0061] R which is a substituted piperidyl group having 5 to 10 carbon atoms 1 Preferable specific examples thereof include a 2-piperidyl group, 3-piperidyl group, 2-(1,2,3,6-tetrahydro)piperidyl group, 2-(1-methyl)piperidyl group, 2-(1-ethyl)piperidyl group, 2-(4-methyl)piperidyl group, 2-(5-methyl)piperidyl group, and 2-(6-methyl)piperidyl group. Among these, more preferable are a 2-piperidyl group, 3-piperidyl group, 2-(1,2,3,6-tetrahydro)piperidyl group, and 2-(6-methyl)piperidyl group, and particularly preferable are a 2-piperidyl group and 2-(1,2,3,6-tetrahydro)piperidyl group.

[0062] R which is a substituted hydrofuryl group having 4 to 10 carbon atoms 1Preferred specific examples of [it] include a 2-tetrahydrofuryl group, a 3-tetrahydrofuryl group, a 2-(5-methyl)tetrahydrofuryl group, a 2-(5-isopropyl)tetrahydrofuryl group, a 2-(5-ethyl)tetrahydrofuryl group, a 2-(5-methoxy)tetrahydrofuryl group, a 2-(5-acetyl)tetrahydrofuryl group, and a 2-(4,5-benzo)tetrahydrofuryl group. Among these, more preferred are a 2-tetrahydrofuryl group, a 3-tetrahydrofuryl group, a 2-(5-methyl)tetrahydrofuryl group, a 2-(5-isopropyl)tetrahydrofuryl group, and a 2-(4,5-benzo)tetrahydrofuryl group, and particularly preferred are a 2-tetrahydrofuryl group, a 2-(5-methyl)tetrahydrofuryl group, and a 2-(5-isopropyl)tetrahydrofuryl group.

[0063] R which is a substituted imidazolyl group having 4 to 10 carbon atoms 1 Preferred specific examples of [it] include a 2-imidazolyl group, a 2-(1-methyl)imidazolyl group, a 2-(1-benzyl)imidazolyl group, a 2-(1-acetyl)imidazolyl group, a 2-(4,5-benzo)imidazolyl group, and a 2-(1-methyl-4,5-benzo)imidazolyl group. Among these, more preferred are a 2-imidazolyl group, a 2-(1-methyl)imidazolyl group, and a 2-(4,5-benzo)imidazolyl group, and particularly preferred are a 2-(1-methyl)imidazolyl group and a 2-(4,5-benzo)imidazolyl group.

[0064] R which is an alkylthio group having 1 to 10 carbon atoms 1 Preferred specific examples of [it] include a methylthio group, an ethylthio group, a propylthio group, and a t-butylthio group. R which is an arylthio group having 6 to 10 carbon atoms 1 Preferred specific examples of [it] include a phenylthio group. Among these, more preferred are a methylthio group, a t-butylthio group, and a phenylthio group, and particularly preferred are a methylthio group and a phenylthio group.

[0065] R which is a halogen atom 1Preferable specific examples thereof include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a chlorine atom is more preferable.

[0066] Among these R 1 Among the preferable groups as R, more preferably, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms are used, and an acyloxy group having 2 to 10 carbon atoms is particularly preferable. Among the acyloxy groups having 2 to 10 carbon atoms, an acyloxy group having 2 to 5 carbon atoms is more preferable.

[0067] In the general formula (1), the value of n is preferably 0 or 1, and more preferably 1.

[0068] Specific examples of particularly preferable polar comonomers represented by the general formula (1) include methyl acrylate, ethyl acrylate, allyl acetate, and allyl methyl ether.

[0069] In the method for producing the (co)polymer of the present invention, the olefin having a polar group represented by the general formula (1) copolymerized with ethylene may be polymerized by combining two or more kinds thereof.

[0070] In the method for producing the (co)polymer of the present invention, in addition to ethylene and the olefin having a polar group represented by the general formula (1), another monomer (third monomer) may be used. Examples of the third monomer include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene. Among these, propylene, 1-butene, and 1-hexene are preferable. These third monomers may be polymerized by combining two or more kinds thereof. However, when an α-olefin is copolymerized as the third monomer, the ratio of the α-olefin to the total of the α-olefin and ethylene contained in the obtained polymer is less than 40 mol%.

[0071] [Polymerization method] The method of polymerizing ethylene alone or ethylene and the monomer represented by the general formula (1) using the metal complex of the present invention as a catalyst is not particularly limited and may be a commonly used polymerization method. That is, process methods such as solution polymerization method, suspension polymerization method, and gas phase polymerization method can be used, and particularly the solution polymerization method and the suspension polymerization method are preferred. The polymerization mode can be either batch mode or continuous mode. The polymerization can be carried out either in one stage or in multiple stages.

[0072] Two or more metal complex catalysts represented by the general formula (C1) may be mixed and used in the polymerization reaction. By using a mixture of metal complex catalysts, it is possible to control the molecular weight, molecular weight distribution, and the content of monomer units derived from the monomer of the general formula (1), thereby obtaining a polymer suitable for a desired application. The molar ratio of the total amount of the metal complex catalyst to the total amount of the monomer is the monomer / metal complex ratio, usually in the range of 1 to 10,000,000, preferably in the range of 10 to 1,000,000, more preferably in the range of 100 to 100,000.

[0073] The polymerization temperature is not particularly limited, but is usually in the range of -30 to 400 °C, preferably in the range of 0 to 200 °C, more preferably in the range of 30 to 180 °C.

[0074] Regarding the polymerization pressure in which the ethylene pressure occupies most of the internal pressure, it is in the range from normal pressure to 100 MPa, preferably in the range from normal pressure to 20 MPa, more preferably in the range from normal pressure to 10 MPa.

[0075] The polymerization time can be appropriately adjusted according to the process mode, the polymerization activity of the catalyst, etc., and a short reaction time of several tens of seconds to several minutes, or a long reaction time of several thousand hours is possible.

[0076] In order to prevent the activity of the catalyst from decreasing, the atmosphere in the polymerization system is preferably filled with an inert gas such as nitrogen gas or argon so that air, oxygen, moisture, etc. other than the monomer do not mix in. In the case of solution polymerization, it is possible to use an inert solvent in addition to the monomer. The inert solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, and tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; aliphatic esters such as methyl acetate and ethyl acetate; and aromatic esters such as methyl benzoate and ethyl benzoate.

Example

[0077] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.

[0078] [Analysis method of polymer structure] The number average molecular weight and weight average molecular weight of the (co)polymer were calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 °C, detector: RI) using a high-temperature GPC apparatus HLC-8121GPC / HT manufactured by Tosoh Corporation equipped with two Showa Denko KK-made AT-806MS columns (connected in series) and using polystyrene as a molecular weight standard substance.

[0079] The content of the monomer unit derived from the olefin having a polar group represented by the general formula (1) was determined by 1H-NMR at 120 °C using JNM-ECS400 manufactured by JEOL Ltd. and using 1,1,2,2-tetrachloroethane-d2 as a solvent. 1 It was determined by 1H-NMR.

[0080] [Synthesis of metal complex 1] Metal complex 1 was synthesized according to the following reaction formula.

Chemical formula

[0081] (a) Synthesis of Isobutyl 2,5-dichloro-3-thiophenesulfonate Under a nitrogen gas atmosphere, 2,5-dichloro-3-thienylsulfonyl chloride (manufactured by Aldrich, 10.8 g, 43.0 mmol) and dehydrated methylene chloride (150 mL) were added to a eggplant flask and stirred in an ice bath. Anhydrous pyridine (6.93 mL, 86.1 mmol) and isobutanol (4.77 mL, 51.6 mmol) were slowly added dropwise thereto. After stirring for 10 minutes, the ice bath was removed and stirring was continued at room temperature for another 18 hours. After quenching the reaction solution by adding 1.0 M hydrochloric acid (100 mL), a liquid separation operation was performed. The organic layer was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a yellow oily substance. The residue was purified by flash column chromatography using methylene chloride as a solvent to obtain isobutyl 2,5-dichloro-3-thiophenesulfonate as a colorless oily substance (7.83 g, yield 63%). 1 H-NMR(400MHz,CDCl3):δ7.14(s,1H),3.94(d,J=6.7Hz,2H),2.02(do,J=13.4,6.7Hz,1H),0.96(d,J=6.7Hz,6H).

[0082] (b) Synthesis of Isobutyl 2,5-dichloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 1a In a nitrogen gas atmosphere, isobutyl 2,5-dichloro-3-thiophenesulfonate (7.83 g, 27.1 mmol), bis(2-methoxyphenyl)phosphine chloride (8.36 g, 29.8 mmol), and dehydrated tetrahydrofuran (20 mL) were added to a nas flask and stirred for 20 minutes in an ice bath. 2,2,6,6-Tetramethylpiperidylmagnesium chloride-lithium chloride (0.62 M tetrahydrofuran solution, 48.0 mL, 29.8 mmol) was slowly added dropwise, and then the mixture was stirred for an additional 1.5 hours. After concentration under reduced pressure, 1.0 M hydrochloric acid (50 mL) and methylene chloride (100 mL) were added to the residue to dissolve it, and the organic layer and the aqueous layer were separated using a separatory funnel. The organic layer was washed with saturated brine and dried over sodium sulfate, and then the solvent was distilled off using a rotary evaporator to obtain a yellow solid. The residue was purified by flash column chromatography using methylene chloride as the solvent to obtain isobutyl 2,5-dichloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 1a as a colorless solid (11.59 g, yield 80%). 1 H-NMR(400MHz,CD2Cl2):δ7.39-7.34(m,2H),6.97-6.84(m,6H),3.89(d,J=6.7Hz,2H),3.76(s,6H),1.83(do,J=13.5,6.7Hz,1H),0.86(d,J=6.7Hz,6H). 31 P-NMR(162MHz,CD2Cl2):δ-31.70.

[0083] (c) Synthesis of metal complex 1 Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 1a (105.4 mg, 0.20 mmol), PdMeCl(cod) (cod = 1,5-cyclooctadiene, 52.4 mg, 0.20 mmol) and dehydrated methylene chloride (2 mL) were added to a eggplant flask and stirred at room temperature for 1 hour. A solution of 2,6-lutidine (68.7 μL, 0.59 mmol) in methylene chloride (2 mL) was added to the solution, and the mixture was further stirred at room temperature for 5.5 hours. After stopping the stirring, anhydrous hexane (8 mL) was slowly added dropwise to the reaction solution, and the mixture was allowed to stand at room temperature for 22 hours. The precipitated colorless crystals were collected by filtration and dried under reduced pressure to obtain metal complex 1 (130.5 mg, yield 94%). 1 H-NMR(400MHz,CD2Cl2):δ7.63(t,J=7.7Hz,1H),7.59-7.53(m,2H),7.45(ddd,J=13.6,7.7,1.7Hz,2H),7.18(d,J=7.7Hz,2H),7.06-7.00(m,4H),3.85(s,6H),3.10(s,6H),-0.01(d,J=3.6Hz,3H). 31 P-NMR(162MHz,CD2Cl2):δ8.08.

[0084] [Synthesis of Metal Complex 2] Metal complex 2 was synthesized according to the following reaction formula. [Chemical Formula]

[0085] (d) Synthesis of isobutyl 5-chloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 2a Under a nitrogen gas atmosphere, 2,5-dichloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonic acid isobutyl 1a (1.00 g, 1.87 mmol) produced by the method described in the section on the synthesis of the metal complex 1, magnesium turnings (50.1 mg, 2.06 mmol), and anhydrous tetrahydrofuran (5 mL) were added to a round-bottom flask and stirred at room temperature for 25 hours. Anhydrous methanol (2 mL) was added, and after stirring for 5 minutes, the solvent was concentrated under reduced pressure. The residue was dissolved in anhydrous toluene (20 mL), filtered through celite (dried diatomaceous earth), and then the solvent was concentrated under reduced pressure to obtain a pale yellow solid. Methylene chloride (20 mL), saturated aqueous ammonium chloride solution (5 mL), and deionized water (10 mL) were added to the residue, and the organic layer and the aqueous layer were separated using a separatory funnel. The aqueous layer was extracted 4 times with methylene chloride (10 mL), and then the combined organic layers were dried over sodium sulfate and the solvent was concentrated using a rotary evaporator. The residue was dried under reduced pressure to obtain 5-chloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonic acid isobutyl 2a as a colorless solid (0.87 g, yield 93%). 1 H-NMR(400MHz,C6D6):δ7.60(d,J=3.3Hz,1H),7.19(ddd,J=7.6,4.0,1.7Hz,2H),7.13-7.08(m,2H),6.83-6.76(m,2H),6.51-6.47(m,2H),3.97(d,J=6.6Hz,2H),3.23(s,6H),1.62(do,J=13.5,6.8Hz,1H),0.62(d,J=6.7Hz,6H). 31 P-NMR(162MHz,C6D6):δ-38.60.

[0086] (e) Synthesis of Metal Complex 2 Under a nitrogen gas atmosphere, 282.3 mg (0.57 mmol) of isobutyl 5-chloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 2a, 150.0 mg (0.57 mmol) of PdMeCl(cod) (cod = 1,5-cyclooctadiene), and 2 mL of dehydrated methylene chloride were added to a round-bottom flask and stirred at room temperature for 10 minutes. 197.0 μL (1.70 mmol) of 2,6-lutidine was added to the solution, and the mixture was further stirred at room temperature for 14 hours. 12 mL of methylene chloride was added to the reaction solution, and after filtration through a glass filter, 30 mL of hexane was slowly added to the filtrate and allowed to stand for 24 hours. The precipitated crystals were collected by filtration, washed with 2 mL of hexane, and dried under reduced pressure to obtain metal complex 2 (372.1 mg, yield 88%). 1 H-NMR(400MHz,CD2Cl2):δ7.71(ddd,J=14.6,7.6,1.7Hz,2H),7.67-7.62(m,2H),7.57-7.53(m,2H),7.19(d,J=7.7Hz,2H),7.07-7.02(m,2H),7.02-6.96(m,2H),3.81(s,6H),3.14(s,6H),-0.06(d,J=4.1Hz,3H). 31 P-NMR(162MHz,CD2Cl2):δ8.01.

[0087] [Synthesis of Metal Complex 3] Metal complex 3 was synthesized according to the following reaction formula.

Chemical Formula

[0088] (f) Synthesis of isobutyl 4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 3a Under a nitrogen gas atmosphere, 2,5-dichloro-4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonic acid isobutyl 1a (1.00 g, 1.87 mmol) prepared by the method described in the section on the synthesis of the metal complex 1, magnesium turnings (91.1 mg, 3.75 mmol), and anhydrous tetrahydrofuran (15 mL) were added to a round-bottom flask, and stirring was started at room temperature. After adding palladium carbon (10% by mass, 39.9 mg), anhydrous methanol (15 mL) was added, and the mixture was stirred overnight. 31 After confirming the completion of the reaction by 31P-NMR spectrum, the solvent was distilled off under reduced pressure. Saturated aqueous ammonium chloride solution (20 mL) and deionized water (10 mL) were added to the residue, and the organic layer and the aqueous layer were separated. The aqueous layer was extracted 4 times with methylene chloride (10 mL), and the combined organic layers were dried over sodium sulfate and then the solvent was distilled off under reduced pressure. Toluene (20 mL) was added to the residue, and after passing through silica gel (3 cm), concentration and drying under reduced pressure were carried out to obtain 4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonic acid isobutyl 3a as a colorless solid (0.59 g, yield 64%). 1 1H-NMR (400 MHz, C6D6): δ 7.90 - 7.87 (m, 1H), 7.13 - 7.07 (m, 2H), 6.99 - 6.91 (m, 2H), 6.75 (t, J = 7.4 Hz, 2H), 6.58 (d, J = 3.4 Hz, 1H), 6.46 (dd, J = 8.2, 5.0 Hz, 2H), 3.96 (d, J = 6.5 Hz, 2H), 3.15 (s, 6H), 1.69 (do, J = 13.3, 6.7 Hz, 1H), 0.70 (d, J = 6.7 Hz, 6H). 31 31P-NMR (162 MHz, C6D6): δ -40.75.

[0089] (g) Synthesis of metal complex 3 Under a nitrogen gas atmosphere, isobutyl 4-bis(2-methoxyphenyl)phosphino-3-thiophenesulfonate 3a (150.0 mg, 0.31 mmol), PdMeCl(cod) (cod = 1,5-cyclooctadiene, 81.2 mg, 0.31 mmol), and dehydrated methylene chloride (4 mL) were added to a round-bottom flask and stirred at room temperature for 40 minutes. 2,6-Lutidine (107.0 μL, 0.91 mmol) was added to the solution, and the mixture was further stirred at room temperature for 36 hours. After filtering the reaction solution through a glass filter, hexane (8 mL) was slowly added to the filtrate and allowed to stand for 21 hours. The precipitated crystals were collected by filtration, washed with hexane (2 mL), and dried under reduced pressure to obtain metal complex 3 (150.1 mg, yield 76%). 1 H-NMR(400MHz,CD2Cl2):δ7.82-7.80(m,1H),7.77-7.62(m,3H),7.61-7.57(m,2H),7.27(dd,J=6.7,3.3Hz,1H),7.22(d,J=7.7Hz,2H),7.12-7.07(m,2H),7.06-7.02(m,2H),3.77(s,6H),3.17(s,6H),0.10(d,J=3.9Hz,3H). 31 P-NMR(162MHz,CD2Cl2):δ8.16.

[0090] [Synthesis of Metal Complex 4] Metal complex 4 was synthesized according to the following reaction formula.

Chemical formula

[0091] (h) Synthesis of isobutyl 2,5-dichloro-4-diisopropylphosphino-3-thiophenesulfonate 4a Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-3-thiophenesulfonate (0.86 g, 3.0 mmol) and dehydrated THF (3 mL) were added to a 50 mL Schlenk tube and cooled in an ice bath. To this solution was added a solution of 2,2,6,6-tetramethylpiperidinylmagnesium chloride-lithium chloride complex·THF solution (concentration 1.0 M, 3.5 mL, 3.5 mmol), and the mixture was stirred for 15 minutes. Further, diisopropylphosphine chloride (0.45 g, 3.0 mmol) was added over 5 minutes, and the mixture was stirred for 2.5 hours. The solvent was distilled off, dehydrated methylene chloride and nitrogen-bubbled 1 M hydrochloric acid were added, and the mixture was stirred vigorously. After the organic layer was dehydrated with sodium sulfate, the solvent was partially distilled off to precipitate a colorless solid. After removing the precipitated solid by filtration, concentration and drying under vacuum gave isobutyl 2,5-dichloro-4-diisopropylphosphino-3-thiophenesulfonate 4a as an orange oil (1.5 g, yield 95%). 1 1H-NMR (400 MHz, CDCl3): δ 3.96 (d, J = 6.4 Hz, 2H), 2.73 (oct, J = 7.0 Hz, 2H), 2.05 (sept, J = 6.4 Hz, 1H), 1.20 (dd, J = 6.8, 17.2 Hz, 6H), 0.97 (d, J = 6.8 Hz, 6H), 0.92 (dd, J = 7.2, 12.8 Hz, 6H). 31 31P-NMR (162 MHz, CDCl3): δ 10.4 ppm.

[0092] (i) Synthesis of metal complex 4 Under an argon gas atmosphere, isobutyl 2,5-dichloro-4-diisopropylphosphino-3-thiophenesulfonate 4a (0.51 g, 1.0 mmol), PdMeCl(cod) (0.26 g, 1 mmol), and dehydrated methylene chloride (10 mL) were added to a 50 mL Schlenk tube and stirred at room temperature for 1 hour. To this solution was added 2,6-lutidine (0.32 g, 3 mmol), and the mixture was further stirred at room temperature for 6 hours. After adding 9 mL of hexane to this reaction solution, the mixture was allowed to stand for 15 hours. The precipitated white solid was collected by filtration and dried under reduced pressure to obtain metal complex 4 (0.4 g, yield 73%). 1H-NMR (400 MHz, CDCl3): δ 7.56 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 8.0 Hz, 2H), 3.17 - 3.07 (m, 2H), 3.13 (s, 6H), 1.40 (dd, J = 7.2, 17.6 Hz, 6H), 1.34 (dd, J = 4.4, 15.6 Hz, 6H), 0.36 (d, J = 2.4 Hz, 3H). 31 P-NMR (162 MHz, CDCl3): δ 45.0 ppm.

[0093] [Synthesis of Metal Complex 5] Metal complex 5 was synthesized according to the following reaction formula.

Chemical Formula

[0094] (j) Synthesis of Isobutyl 2,5-dichloro-4-dimethylphosphino-3-thiophenesulfonate 5a Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-3-thiophenesulfonate (0.86 g, 3.0 mmol), dimethylchlorophosphine (3.0 mmol), and dehydrated THF (12 mL) were added to a 100 mL Schlenk tube and stirred at -70 °C. A solution of lithium tetramethylpiperidide·THF (3.0 mmol) was added dropwise to this solution, and the mixture was stirred for 2 hours while warming to 0 °C. The reaction solution was concentrated under reduced pressure at room temperature to obtain a light brown oil. The residue was purified by silica gel column chromatography using hexane as the eluent to obtain isobutyl 2,5-dichloro-4-dimethylphosphino-3-thiophenesulfonate 5a as a clear oil (1.08 g, yield 47%). 31 P-NMR (162 MHz, CDCl3): δ -3.2 ppm.

[0095] (k) Synthesis of Metal Complex 5 Under an argon gas atmosphere, isobutyl 2,5-dichloro-4-dimethylphosphino-3-thiophenesulfonate 5a (0.11 g, 0.19 mmol), PdMeCl(cod) (0.048 g, 0.18 mmol), 2,6-lutidine (0.081 g, 0.76 mmol), and dehydrated THF (7 mL) were added to a 10 mL Schlenk tube, and the mixture was stirred at 60 °C for 19 hours. The solvent was distilled off, and the metal complex 5 was obtained as a white solid by reprecipitation with THF / hexane (0.055 g, yield 38%). 1 H-NMR(400MHz,CDCl3):δ7.56(t,J=3.9Hz,1H),7.12-7.06(m,2H),3.17(s,3H),3.12(s,3H),2.99-2.86(m,2H),2.86-2.78(m,1H),2.26(quintet,J=14.8Hz,1H),2.10-2.05(m,1H),2.03-1.97(m,1H),1.92-1.68(m,6H),1.34-1.24(m,5H),0.96-0.92(m,9H),0.89-0.84(m,9H),0.43(d,J=2.0Hz,3H),0.31(d,J=6.4Hz,3H). 31 P-NMR(162MHz,CDCl3):δ35.0ppm.

[0096] [Synthesis of Metal Complex 6] Metal complex 6 was synthesized according to the following reaction formula.

Chemical formula

[0097] (l) Synthesis of Isobutyl 2,5-Dichloro-4-(Dichlorophosphino)-3-thiophenesulfonate Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-3-thiophenesulfonate (2.0 g, 7.0 mmol) and dehydrated THF (5 mL) were added to a 50 mL Schlenk tube, and the mixture was stirred at -30 °C. To this solution, a solution of 2,2,6,6-tetramethylpiperidinylmagnesium chloride-lithium chloride complex·THF solution (0.75 M, 9.3 mL, 7.0 mmol) was added, and the mixture was stirred for 2.5 hours while warming to room temperature. While stirring a 200 mL three-necked flask containing phosphorus trichloride (1.10 g, 8.0 mmol) and dehydrated THF (20 mL) at -35 °C under a nitrogen gas atmosphere, the above reaction solution was added dropwise, and then the mixture was stirred for 1.5 hours while maintaining the temperature at -40 to -20 °C. The solvent of this solution was distilled off while cooling to -20 °C. The obtained reddish-brown residue was dissolved in dehydrated methylene chloride (10 mL), filtered through celite, and then the filtrate was concentrated to obtain isobutyl 2,5-dichloro-4-(dichlorophosphino)-3-thiophenesulfonate. 1 1H-NMR (400 MHz, CDCl3): δ 3.96 (d, J = 6.4 Hz, 2H), 2.01 (sept, J = 6.7 Hz, 1H), 0.94 (d, J = 6.8 Hz, 6H). 31 31P-NMR (162 MHz, CDCl3): δ 138.2 ppm.

[0098] (m) Synthesis of isobutyl 2,5-dichloro-4-(bis(2-isopropylphenyl)phosphino)-3-thiophenesulfonate 6a Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-4-(dichlorophosphino)-3-thiophenesulfonate (1.0 mmol) and dehydrated THF (5 mL) were added to a 50 mL Schlenk tube and stirred at -65 °C. A solution of 2-isopropylphenylmagnesium bromide·THF (0.43 M, 4.9 mL) was added dropwise to this solution over 30 minutes, and the mixture was stirred for 2 hours while warming to room temperature. After quenching by adding ethanol, the solvent was distilled off to obtain a light brown oil. This residue was purified by silica gel column chromatography using hexane → hexane / THF (11:1) as the eluent to obtain isobutyl 2,5-dichloro-4-(bis(2-isopropylphenyl)phosphino)-3-thiophenesulfonate 6a as a transparent oil (0.18 g, yield 28%). 1 1H-NMR (400 MHz, CDCl3): δ 7.33 (br, 4H), 7.09 (br, 4H), 3.61 (br, 2H), 3.41 (sept, J = 6.8 Hz, 2H), 1.51 (sept, J = 6.8 Hz, 1H), 1.37 - 0.98 (br, 12H), 0.75 (br, 6H). 31 31P-NMR (162 MHz, CDCl3): δ -26.7 ppm.

[0099] (n) Synthesis of metal complex 6 Under an argon gas atmosphere, isobutyl 2,5-dichloro-4-(bis(2-isopropylphenyl)phosphino)-3-thiophenesulfonate 6a (0.11 g, 0.17 mmol), PdMeCl(cod) (0.045 g, 0.17 mmol), 2,6-lutidine (0.055 g, 0.51 mmol), and dehydrated THF (7 mL) were added to a 30 mL Schlenk tube and stirred at 60 °C for 58 hours. After cooling to room temperature, hexane was added to the reaction solution. The precipitated white solid was collected by filtration and dried under reduced pressure to obtain metal complex 6 (0.081 g, yield 58%). 1H-NMR (400 MHz, CDCl3): δ 7.56 (t, J = 3.8 Hz, 1H), 7.51 (t, J = 1.7 Hz, 4H), 7.36 (dd, J = 6.4, 4.0 Hz, 2H), 7.20 - 7.15 (m, 2H), 7.09 (d, J = 4.0 Hz, 2H), 3.87 (br, 2H), 3.06 (s, 6H), 1.34 (d, J = 3.2 Hz, 6H), 1.12 (d, J = 3.6 Hz, 6H), 0.39 (d, J = 1.6 Hz, 3H). 31 P-NMR (162 MHz, CDCl3): δ 13.6 ppm.

[0100] [Synthesis of Metal Complex 7] Metal Complex 7 was synthesized according to the following reaction formula.

Chemical Formula

[0101] [Synthesis of Isobutyl 2,5-dichloro-4-(bis(2,7-di-t-butyl-9-fluorenyl)phosphino)-3-thiophenesulfonate 7a] Under a nitrogen gas atmosphere, 2,7 - di - t - butylfluorene (1.39 g, 5.0 mmol) and dehydrated THF (20 mL) were added to a 50 mL Schlenk tube, and the mixture was stirred while cooling in an ice bath. To this solution, an n - butyllithium - hexane solution (1.6 M, 3.2 mL, 5.1 mmol) was slowly added, and the mixture was stirred for 3 hours while warming to room temperature (this solution is designated as solution A). Under a nitrogen gas atmosphere, a THF solution of isobutyl 2,5 - dichloro - 4 - (dichlorophosphino) - 3 - thiophenesulfonate (0.26 M, 6.8 mL, 1.8 mmol) and dehydrated THF (10 mL) were added to a 100 mL Schlenk tube, and the mixture was stirred at - 75 °C. Solution A (19 mL) was slowly added to this solution, and then the mixture was stirred at - 75 °C for 1 hour and further stirred for 2 hours while warming to room temperature. After quenching by adding ethanol, the solvent was distilled off to obtain a light brown oil. The residue was purified by silica gel column chromatography using THF / hexane (7:3) → THF as the eluent to obtain isobutyl 2,5 - dichloro - 4 - (bis(2,7 - di - tert - butyl - 9 - fluorenyl)phosphino) - 3 - thiophenesulfonate 7a as a brown oil (0.6 g, yield 25%). 31 P - NMR (162 MHz, CDCl3): δ 16.1 ppm.

[0102] (p) Synthesis of metal complex 7 Under an argon gas atmosphere, isobutyl 2,5 - dichloro - 4 - (bis(2,7 - di - t - butyl - 9 - fluorenyl)phosphino) - 3 - thiophenesulfonate 7a (0.25 g, 0.20 mmol), PdMeCl(cod) (0.053 g, 0.20 mmol), 2,6 - lutidine (0.12 mL, 1.0 mmol), and dehydrated methylene chloride (10 mL) were added to a 30 mL Schlenk tube, and the mixture was stirred at room temperature for 2 days. The reaction solution was filtered through Celite, and the resulting filtrate was concentrated. The residue was recrystallized from methylene chloride and diethyl ether to obtain metal complex 7 as a white solid (0.10 g, yield 50%). 11H-NMR (400 MHz, CDCl3): δ 8.39 (s, 1H), 8.33 (s, 1H), 8.23 (s, 1H), 7.87 (d, J = 8 Hz, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.74 (d, J = 8 Hz, 1H), 7.65 (d, J = 8 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.44 - 7.38 (m, 3H), 6.98 - 6.92 (m, 2H), 6.85 (d, J = 8 Hz, 1H), 6.11 (d, J = 18 Hz, 1H), 5.47 (d, J = 4.8 Hz, 1H), 3.08 (s, 3H), 2.15 (s, 3H), 1.36 (s, 9H), 1.34 (s, 9H), 1.26 (s, 9H), 1.10 (s, 9H), 0.04 (d, J = 2.8 Hz, 3H). 31 31P-NMR (162 MHz, CDCl3): δ 22.3 ppm.

[0103] [Synthesis of Metal Complex 8] Metal complex 8 was synthesized according to the following reaction formula.

Chemical Formula

[0104] (q) Synthesis of Isobutyl 2,5-Dichloro-4-(Bis(diphenylmethyl)phosphino)-3-thiophenesulfonate 8a Under a nitrogen gas atmosphere, diphenylmethane (2.5 mL, 15 mmol) and dehydrated THF (25 mL) were added to a 100 mL Schlenk tube, and the mixture was stirred at -70 °C. To this solution, an n-butyllithium hexane solution (1.5 M, 10 mL, 15.0 mmol) was added dropwise at -70 °C, and then the mixture was stirred for 2 hours while warming to room temperature (this solution is designated as solution B). Under a nitrogen gas atmosphere, a THF solution of isobutyl 2,5-dichloro-4-(dichlorophosphino)-3-thiophenesulfonate (0.14 M, 10.7 mL, 1.5 mmol) and dehydrated THF (6 mL) were added to a 300 mL three-necked flask, and the mixture was stirred at -70 °C. Solution B (11.3 mL) was slowly added to this solution, and the mixture was stirred for 2 hours while warming to room temperature. After quenching by adding isobutyl alcohol, the solvent was distilled off. After adding methylene chloride and hexane to the residue, filtration was performed, and the filtrate was concentrated. The residue was purified by silica gel column chromatography using hexane / THF (10:1) → THF as the eluent to obtain isobutyl 2,5-dichloro-4-(bis(diphenylmethyl)phosphino)-3-thiophenesulfonate 8a as an orange solid (0.14 g, yield 20%). 31 P-NMR (162 MHz, CDCl3): δ 0.0 ppm.

[0105] (r) Synthesis of metal complex 8 Under an argon gas atmosphere, isobutyl 2,5-dichloro-4-(bis(diphenylmethyl)phosphino)-3-thiophenesulfonate 8a (0.7 g, 0.32 mmol), PdMeCl(cod) (0.17 g, 0.64 mmol), 2,6-lutidine (0.23 mL, 1.9 mmol), and dehydrated methylene chloride (11 mL) were added to a 50 mL Schlenk tube, and the mixture was stirred at room temperature for 3 days. After filtering the reaction solution through Celite, the filtrate was concentrated. The residue was purified by silica gel column chromatography using hexane → ethyl acetate as the eluent to obtain metal complex 8. 1 H-NMR (400 MHz, CDCl3): δ 7.75 - 6.96 (m, 23H), 4.86 (d, J = 12.0 Hz, 2H), 2.82 (s, 6H), -0.81 (d, J = 2.4 Hz, 3H). 31 P-NMR (162 MHz, CDCl3): δ 36.0 ppm.

[0106] [Synthesis of Metal Complex 9] Metal complex 9 was synthesized according to the following reaction formula.

Chemical Formula

[0107] [Synthesis of Isobutyl 2,5-dichloro-4-di-t-butylphosphino-3-thiophenesulfonate 9a] Under a nitrogen gas atmosphere, isobutyl 2,5-dichloro-3-thiophenesulfonate (2.0 g, 7.0 mmol), di-t-butylchlorophosphine (1.3 mL, 7.0 mmol), and dehydrated THF (30 mL) were added to a 100 mL Schlenk tube, and the mixture was stirred while cooling to -78 °C. A solution of lithium tetramethylpiperidide·THF (concentration 0.35 M) (20 mL, 7.0 mmol) was added dropwise to this solution, and the mixture was stirred overnight while gradually warming to room temperature. Then, the solvent was distilled off with a vacuum pump, dehydrated methylene chloride and degassed aqueous ammonium chloride solution were added, and the mixture was stirred vigorously. After standing, the methylene chloride solution layer was extracted, dried over sodium sulfate, and the solvent was distilled off to obtain isobutyl 2,5-dichloro-4-di-t-butylphosphino-3-thiophenesulfonate 9a (2.1 g, yield 71%). 1 H-NMR (400 MHz, CDCl3): δ 3.92 (d, J = 6.4 Hz, 2H), 2.00 (sept, J = 6.4 Hz, 1H), 1.25 (d, J = 12.4 Hz, 18H), 0.93 (d, J = 6.4 Hz, 6H). 31 P-NMR (162 MHz, CDCl3): δ 21.5 ppm.

[0108] [Synthesis of Metal Complex 9 (t)] Under an argon gas atmosphere, 9a (0.29 g, 0.60 mmol) of isobutyl 2,5-dichloro-4-di-t-butylphosphino-3-thiophenesulfonate, PdMeCl(cod) (0.16 g, 0.60 mmol), 2,6-lutidine (0.21 mL, 1.8 mmol) and dehydrated methylene chloride (20 mL) were added to a 50 mL Schlenk tube and stirred at room temperature for 2 days. After filtration through a syringe filter and evaporation of the solvent, recrystallization from methylene chloride (3 mL) and hexane (5 mL) gave metal complex 9 (0.16 g, 41% yield). 1 1H-NMR (400 MHz, CDCl3): δ 7.58 (t, J = 7.6 Hz, 1H), 7.13 (d, J = 7.8 Hz, 2H), 3.14 (s, 6H), 1.54 (d, J = 15.1 Hz, 18H), 0.55 (d, J = 1.8 Hz, 3H). 31 31P-NMR (162 MHz, CDCl3): δ 52.5 ppm.

[0109] [Synthesis of Comparative Metal Complexes 1-2] (u) Synthesis of Comparative Metal Complex 1 According to the method described in JP-A-2011-68881, the following formula [Chemical formula] was used to synthesize comparative metal complex 1 shown below.

[0110] (v) Synthesis of Comparative Metal Complex 2 According to the method described in WO 2019 / 093364, the following formula [Chemical formula] was used to synthesize comparative metal complex 2 shown below.

[0111] [Synthesis of Polymers] Using metal complexes 1-3 and comparative metal complexes 1-2 synthesized by the above methods, (co)polymerization of olefins was carried out. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively. The productivity and catalytic activity were calculated by the following formulas. [Number] [Number]

[0112] (Example 1): Homopolymerization of ethylene using Metal Complex 1 (Preparation of Polymer 1) Under a nitrogen gas atmosphere, toluene (50 mL) was added to a 120 mL autoclave containing Metal Complex 1 (3.5 mg, 0.0050 mmol). After filling with ethylene (3.0 MPa), the autoclave was stirred at 80 °C for 1 hour. After cooling to room temperature, the reaction solution in the autoclave was added to methanol (300 mL) to precipitate the polymer. The resulting polymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain Polymer 1. The yield was 19.1 g. The productivity was calculated to be 3820 g / mmol, and the catalytic activity was calculated to be 3820 g / (mmol·h). The molecular weight of Polymer 1 was measured by size exclusion chromatography, and the number average molecular weight Mn was 27,800, the weight average molecular weight Mw was 58,700, and Mw / Mn was 2.11.

[0113] (Comparative Example 1): Homopolymerization of ethylene using Comparative Metal Complex 1 (Preparation of Comparative Polymer 1) Ethylene homopolymerization was carried out in the same manner as the method described in Example 1, except that the metal complex used was changed to Comparative Metal Complex 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0114] (Example 2): Copolymerization of allyl acetate and ethylene using Metal Complex 1 (Preparation of Polymer 2) In a 120 mL autoclave containing metal complex 1 (3.5 mg, 0.0050 mmol) under a nitrogen gas atmosphere, toluene (63.4 mL) and allyl acetate (11.6 mL, 108 mmol) as the monomer represented by the general formula (1) were added. After filling with ethylene (4.0 MPa), the autoclave was stirred at 80 °C for 1 hour. After cooling to room temperature, the reaction solution in the autoclave was dried under reduced pressure to obtain polymer 2. The yield was 2.33 g. The productivity was calculated to be 466.7 g / mmol, and the catalytic activity was calculated to be 466.7 g / (mmol·h). The molecular weight of polymer 2 was measured by size exclusion chromatography, and the number average molecular weight Mn was 11,200, the weight average molecular weight Mw was 26,800, and Mw / Mn was 2.39. The allyl acetate content in the copolymer was 1 determined by 1H-NMR measurement to be 100:1.4 in terms of the molar ratio of ethylene:allyl acetate (allyl acetate molar fraction = 1.4%). The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively.

[0115] (Examples 3 - 4): Copolymerization of allyl acetate and ethylene using metal complexes 2 - 3 (Preparation of polymers 3 - 4) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 2, except that the metal complex used was changed to metal complex 2 or 3. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively.

[0116] (Comparative Examples 2 - 3): Copolymerization of allyl acetate and ethylene using comparative metal complexes 1 - 2 (Preparation of comparative polymers 2 - 3) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 2, except that the metal complex used was changed to comparative metal complex 1 or 2. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively.

[0117] (Examples 5 - 10): Homopolymerization of ethylene using metal complexes 4 - 9 (Preparation of polymers 5 - 10) Homopolymerization of ethylene was carried out in the same manner as the method described in Example 1, except that the metal complex used was changed to any one of metal complexes 4 - 9 and the catalyst charge amount was changed. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively.

[0118] (Examples 11 - 16): Copolymerization of allyl acetate and ethylene using metal complexes 4 - 9 (Preparation of polymers 11 - 16) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 2, except that the metal complex used was changed to any one of metal complexes 4 - 9. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0119]

Table 1

[0120]

Table 2

[0121] In the homopolymerization of ethylene, when metal complexes 1, 4 - 9 were used (Examples 1, 5 - 10), compared with the case when comparative metal complex 1 was used (Comparative Example 1), the productivity and catalytic activity were improved.

[0122] In the copolymerization of allyl acetate and ethylene, when metal complexes 1 - 9 were used (Examples 2 - 4, 11 - 16), compared with the case when comparative metal complex 1 or 2 was used (Comparative Examples 2 - 3), the productivity and catalytic activity were improved.

[0123] (Example 17): Copolymerization of allyl acetate and ethylene using metal complex 1 (Preparation of polymer 17) In order to make the allyl acetate content in the copolymer of allyl acetate and ethylene about 20 mol%, copolymerization of allyl acetate and ethylene was attempted without using a solvent. In this case, allyl acetate also serves as a solvent. Under a nitrogen gas atmosphere, allyl acetate (75.0 mL) was added to a 120 mL autoclave containing metal complex 1 (7.0 mg, 0.010 mmol). After filling with ethylene (1.6 MPa), the autoclave was stirred at 65 °C for 24 hours. After cooling to room temperature, the reaction solution in the autoclave was added to methanol (300 mL) to precipitate the polymer. The resulting polymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain Polymer 17. The yield was 0.97 g. The productivity was calculated to be 96.9 g / mmol, and the catalytic activity was calculated to be 4.0 g / (mmol·h). The molecular weight of Polymer 17 was measured by size exclusion chromatography, and the number average molecular weight Mn was 800, the weight average molecular weight Mw was 1,900, and Mw / Mn was 2.37. The allyl acetate content in the copolymer was 1 determined by 1H-NMR measurement to be 100:26.1 in the molar ratio of ethylene:allyl acetate (allyl acetate molar fraction = 20.7%). The polymerization conditions and polymerization results are shown in Tables 3 and 4, respectively.

[0124] (Examples 18 - 19): Copolymerization of allyl acetate and ethylene using metal complexes 5 - 6 (Preparation of Polymers 18 - 19) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 17, except that the metal complex used was changed to metal complex 5 or 6, and the ethylene pressure for charging was changed with the target of 20 mol% of the allyl acetate molar fraction in the copolymer. The polymerization conditions and polymerization results are shown in Tables 3 and 4, respectively.

[0125] (Comparative Examples 4 - 5): Copolymerization of allyl acetate and ethylene using comparative metal complexes 1 - 2 (Preparation of Comparative Polymers 4 - 5) The copolymerization of allyl acetate and ethylene was attempted in the same manner as the method described in Example 17, except that the metal complex used was replaced with Comparative Metal Complex 1 or 2. However, no polymer was formed. In Comparative Examples 4 and 5, since the relative amount of allyl acetate was increased, it is presumed that Comparative Metal Complex 1 and Comparative Metal Complex 2 were deactivated. The polymerization conditions and polymerization results are shown in Tables 3 and 4, respectively. Since no copolymer was obtained, the measured values of the molecular weight and the allyl acetate unit content are blank.

[0126]

Table 3

[0127]

Table 4

[0128] In the copolymerization of allyl acetate and ethylene, where the target is that the allyl acetate unit content in the copolymer is around 20 mol%, when using Metal Complex 1, 5, or 6 (Examples 17 to 19), the productivity and catalytic activity were improved compared to the case of using Comparative Metal Complex 1 or 2 (Comparative Examples 4 to 5).

[0129] From the above Examples and Comparative Examples, it was found that in the polymerization of olefins containing allyl monomers having a polar group, the metal complex catalyst of the present disclosure has higher catalytic activity compared to conventional metal complex catalysts. That is, the production cost of olefin polymers containing allyl monomers having a polar group can be reduced by the metal complex catalyst of the present disclosure.

Claims

1. General formula (C1) 【Chemical 1】 (In the formula, M represents a palladium atom or a nickel atom, and X represents a phosphorus atom (P). R ５ represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R ６ and R ７ each independently represent a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group. R ８ and R ９ each independently represent a hydrogen atom or a halogen atom. L represents an electron-donating ligand, and q is 0, 1 / 2, 1, or 2.) A catalyst for olefin polymerization containing a metal complex represented by the formula.

2. R in the general formula (C1) ８ and R ９ are each independently a hydrogen atom or a chlorine atom, and the olefin polymerization catalyst according to claim 1.

3. R in the general formula (C1) ８ and R ９ The olefin polymerization catalyst according to claim 2, wherein one of them is a hydrogen atom and the other is a chlorine atom.

4. R in the general formula (C1) ８ and R ９ The olefin polymerization catalyst according to claim 2, wherein both are chlorine atoms.

5. R in the general formula (C1) ６ and R ７ are each independently an alkyl group, a fluoroalkyl group, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, The olefin polymerization catalyst according to any one of claims 1 to 4.

6. R in the general formula (C1) ６ and R ７ are both isopropyl group, t-butyl group, menthyl group, 2,7-di-t-butyl-9-fluorenyl group, diphenylmethyl group, 2-methoxyphenyl group, or 2-isopropylphenyl group. The olefin polymerization catalyst according to any one of claims 1 to 4

7. General formula (C1) [Chemical 2] (In the formula, M represents a palladium atom or a nickel atom, and X represents a phosphorus atom (P). R5 represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R6 and R7 each independently represent a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group. R8 and R9 each independently represent a hydrogen atom or a halogen atom. L represents an electron-donating ligand, and q is 0, 1 / 2, 1, or 2.) Using the metal complex represented by as a polymerization catalyst, a homopolymer of ethylene, ethylene and general formula (1) 【Chemical Formula 3】 (In the formula, R １ represents a substituent selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R—O—(C═O)—, where R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, a substituted amide group having 2 to 12 carbon atoms, a substituted pyridyl group having 5 to 10 carbon atoms, a substituted pyrrolidyl group having 4 to 10 carbon atoms, a substituted piperidyl group having 5 to 10 carbon atoms, a substituted hydrofuryl group having 4 to 10 carbon atoms, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. n is an integer selected from 0 to 6.) A method for producing a copolymer with an olefin having a polar group represented by the formula, or a copolymer of ethylene, an olefin having a polar group represented by the general formula (1), and another monomer.)

8. The method according to claim 7, wherein n in general formula (1) is 0.

9. The method according to claim 7, wherein n in general formula (1) is 1.

10. R in the general formula (C1) ８ and R ９ are each independently a hydrogen atom or a chlorine atom, the method according to any one of claims 7 to 9.

11. R in the general formula (C1) ８ and R ９ The method according to claim 10, wherein one of them is a hydrogen atom and the other is a chlorine atom.

12. R in the general formula (C1) ８ and R ９ are both chlorine atoms, the method according to claim 10.

13. R in the general formula (C1) ６ and R ７ are each independently an alkyl group, a fluoroalkyl group, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, the method according to any one of claims 7 to 9.

14. R in the general formula (C1) ６ and R ７ The method according to any one of claims 7 to 9, wherein both are an isopropyl group, a t-butyl group, a menthyl group, a 2,7-di-t-butyl-9-fluorenyl group, a diphenylmethyl group, a 2-methoxyphenyl group, or a 2-isopropylphenyl group.

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