Metal complex, and olefin polymerization catalyst component and olefin polymerization catalyst that contain that metal complex, and method for producing olefin polymer using that olefin polymerization catalyst

Abstract

To provide: a highly active metal complex for use in the production of olefinic (particularly propylene) polymers and copolymers without a decrease in molecular weight compared to conventional catalysts; an olefin polymerization catalyst component and an olefin polymerization catalyst that contain the metal complex; and a method for producing an olefin polymer using the olefin polymerization catalyst.SOLUTION: A metal complex represented by general formula [1] is used, where L1 is an auxiliary ligand and, specifically, represents a compound represented by general formula [2].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a metal complex, an olefin polymerization catalyst component and an olefin polymerization catalyst each containing the metal complex, and a process for producing an olefin polymer using the olefin polymerization catalyst. [Background technology]

[0002] Copolymers of olefins and vinyl monomers containing polar functional groups are industrially useful polymers. These copolymers are generally produced by high-pressure radical polymerization. Although high-pressure radical polymerization is effective for the polymerization of ethylene, it cannot polymerize olefins having a large number of carbon atoms such as propylene. Coordination polymerization is also widely known as a method for producing ethylene and olefin polymers. Ziegler catalysts and metallocene catalysts are widely used in coordination polymerization, but these catalysts are deactivated by vinyl monomers containing polar functional groups. Therefore, it has been difficult to obtain copolymers with polar functional 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 functional group-containing vinyl monomer, the use of a late transition metal complex catalyst makes it difficult for deactivation caused by the polar functional group-containing vinyl monomer to occur, and copolymerization proceeds. 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). It is also known that auxiliary ligands affect the performance of olefin polymerization catalysts. As a specific example, Mecking et al. reported that the catalytic activity of a nickel complex having a salicylaldimine ligand was improved by changing the auxiliary ligand from pyridine to N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as TMEDA) or dimethylformamide (hereinafter referred to as DMF) (Non-Patent Document 3). Claverie et al. reported that, in a palladium complex having a phosphine sulfonate ligand, a complex having pyridine as an auxiliary ligand and a complex having TMEDA as an auxiliary ligand have a higher catalytic activity in ethylene homopolymerization than a complex having the latter (Non-Patent Document 4). 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). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6913051 [Patent Document 2] International Publication No. 2018 / 021446 [Non-patent literature]

[0004] [Non-Patent Document 1] M. Brookhart et al., "J. Am. Chem. Soc.", 1996, 118, 267-268. [Non-Patent Document 2] RH Grubbs et al., Science, 2000, 287, 460-462. [Non-Patent Document 3] S. Mecking et al., ACS Catalysis, 2019, 9, 11552-11556. [Non-Patent Document 4] JPClaverie et al., Macromol.Rapid Commun., 2007, 28, 2033-2038. Summary of the Invention [Problem to be solved by the invention]

[0005] In industrially producing a copolymer of an olefin having 3 or more carbon atoms, such as propylene, and a vinyl monomer containing a polar functional group, the catalytic activity of the metal complex disclosed in Patent Document 2 is not sufficient. Therefore, there is a demand for the development of a complex catalyst with higher activity while maintaining the molecular weight of the obtained polymer. One method for improving the activity of a complex catalyst is to change the auxiliary ligand. For example, in Patent Document 2, pyridine, triethylphosphine, or the olefin moiety of a (1,4,5,-η)-4-cycloocten-1-yl group is used as the auxiliary ligand. However, as mentioned above, the catalytic activity of these metal complex catalysts is insufficient. Non-Patent Documents 3 and 4 report that activity can be improved by changing the auxiliary ligand from pyridine to TMEDA, but this has problems such as a decrease in molecular weight and insufficient catalytic activity.

[0006] In view of the above-mentioned problems of the conventional technology, an object of the present invention is to provide a highly active metal complex that can be used for producing olefin (particularly propylene) polymers and copolymers without causing a decrease in molecular weight as compared with conventional catalysts, an olefin polymerization catalyst component and an olefin polymerization catalyst containing the metal complex, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Means for solving the problem]

[0007] That is, the present invention includes the following aspects. <1> A metal complex represented by the following general formula [1].

[0008] [ka]

[0009] [In formula 1, R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 11 , CO2R 11 , CO2M', C(O)N(R 12 )2, C(O)R 11 , O.C.(O)R 11 , S.R. 11 , SO2R 11 , OSO2R 11 , P(O)(OR 11 ) 2-y (R 11 ) y , C.N., N.R. 11 (R 12 ), Si(OR 12 ) 3-x (R 12 ) x , OSi(OR 12 ) 3-x (R 12 ) x , NO2, SO3M', PO3M'2, P(O)(OR 12 )2M', or an epoxy-containing group. R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 11 and R 12 If there are multiple R 11 and R 12 may be the same or different. 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. R 1 , R 2 , R3 and R 4 may be bonded to each other to form a ring. R 5 and R 6 each independently represents 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; NR 11 (R 12 ), or SiR 11 (R 12 )2 (where R 12 may be the same or different. R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom or a sulfur atom. M represents nickel or palladium. L 1 is an auxiliary ligand and represents a compound represented by the general formula [2]. [In formula [2], R 8 , R 9 and R 10 are each independently N(R 11 )2 (where R 11 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 11 has the same definition as above, except that R 8 , R 9 and R 10 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 8 , R 9 and R 10 may be bonded to each other to form an alicyclic structure.

[0010] <2> R 8 , R 9 and R 10 are each independently, N(R 11 )2 (where R 11 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (wherein R 8 , R 9 and R 10 When any two of the above are aryl groups having 6 to 12 carbon atoms, the remaining one cannot be an aryl group having 6 to 12 carbon atoms. <1> The metal complex according to claim 1.

[0011] <3> The total number of nitrogen atoms contained in the compound represented by the general formula [2] is 3 or less. <1> The metal complex according to claim 1.

[0012] <4> R 5 and R 6 each independently represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may have at least one selected from the group consisting of a heteroatom and a group containing a heteroatom, <1> The metal complex according to claim 1.

[0013] <5> R 5 and R 6 are each independently a branched acyclic alkyl group having 3 to 20 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or an aryl group having 6 to 15 carbon atoms, <1> The metal complex according to claim 1.

[0014] <6> The above <1> ~ <5> 13. A catalyst component for olefin polymerization, comprising the metal complex according to any one of claims 1 to 12.

[0015] <7> The above <1> ~ <5> 13. An olefin polymerization catalyst comprising the metal complex according to claim 12.

[0016] <8> The above <6> 2. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst component according to claim 1.

[0017] <9> The above <7> 2. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to claim 1. Effect of the Invention

[0018] According to the present invention, it is possible to provide a highly active metal complex that can be used for producing an olefin (particularly propylene) polymer or copolymer without a decrease in molecular weight as compared with conventional catalysts, an olefin polymerization catalyst component and an olefin polymerization catalyst containing the metal complex, and a method for producing an olefin polymer using the olefin polymerization catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The present invention provides a metal complex represented by general formula [1], an olefin polymerization catalyst component containing the metal complex, a catalyst containing the metal complex as a catalyst component, and a method for producing an olefin polymer or copolymer in the presence of the catalyst. In the present invention, "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, "(meth)acrylic acid ester" includes both acrylic acid ester and methacrylic acid ester. In addition, in this specification, the use of "to" indicating a numerical range is used to mean that the numerical 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 that it is a normal structure.

[0020] 1. Metal complexes According to the present invention, there is provided a metal complex represented by the following general formula [1]:

[0021] [ka]

[0022] [In formula 1, R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 11 , CO2R 11 , CO2M', C(O)N(R 12 )2, C(O)R 11 , O.C.(O)R 11 , S.R. 11 , SO2R 11 , OSO2R 11 , P(O)(OR 11 ) 2-y (R 11 )y , C.N., N.R. 11 (R 12 ), Si(OR 12 ) 3-x (R 12 ) x , OSi(OR 12 ) 3-x (R 12 ) x , NO2, SO3M', PO3M'2, P(O)(OR 12 )2M', or an epoxy-containing group. R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 11 and R 12 If there are multiple R 11 and R 12 may be the same or different. 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. R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring. R 5 and R 6 each independently represents 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; NR 11 (R 12 ), or SiR 11 (R 12 )2 (where R 12 may be the same or different. R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom or a sulfur atom. M represents nickel or palladium. L 1is an auxiliary ligand and represents a compound represented by the general formula [2]. [In formula [2], R 8 , R 9 and R 10 are each independently N(R 11 )2 (where R 11 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 11 has the same definition as above, except that R 8 , R 9 and R 10 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 8 , R 9 and R 10 may be bonded to each other to form an alicyclic structure.

[0023] By using the metal complex of the present invention, olefin (co)polymers, particularly propylene (co)polymers, can be obtained with high activity and without a decrease in molecular weight as compared with conventional catalysts. When a tertiary amine, a compound represented by the general formula [2] that is basic, has low π-acceptance, has no protons, and has a moderate coordination power that is not sterically bulky around the nitrogen atom, is used as one of the components of an olefin polymerization catalyst, the tertiary amine acts as an auxiliary ligand to prevent the complex from decomposing, while it is easily detached from the central metal during the polymerization reaction, making it easier for the activation reaction to proceed, and the initiation efficiency of polymerization increases, resulting in high activation without changing the molecular weight. In addition, since there is no change in the physical properties of the olefin (co)polymer when the compound represented by the general formula [2] is used in combination with or without it, it is presumed that the high activation is not due to the deterioration of the active sites of the olefin polymerization catalyst.

[0024] General formulas [1] and [2] will be explained below.

[0025] [General formula [1]] R 1 , R 2 , R 3 and R 4 each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) Halogen atom (iii) a hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom. (iv) OR 11 , CO2R 11 , CO2M', C(O)N(R 12 )2, C(O)R 11 , O.C.(O)R 11 , S.R. 11 , SO2R 11 , OSO2R 11 , P(O)(OR 11 ) 2-y (R 11 ) y , C.N., N.R. 11 (R 12 ), Si(OR 12 ) 3-x (R 12 ) x , OSi(OR 12 ) 3-x (R 12 ) x , NO2, SO3M', PO3M'2, P(O)(OR 12 )2M', or an epoxy-containing group. R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 11 and R 12 If there are multiple R 11 and R 12 may be the same or different. 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. R 1 , R 2 , R 3 and R 4may be bonded to each other to form a ring.

[0026] (ii) Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred.

[0027] Examples of the hydrocarbon group having 1 to 30 carbon atoms in (iii) 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 acyclic alkyl groups having 3 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, arylalkyl groups having 7 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkenyl groups having 3 to 30 carbon atoms which may have a side chain, aryl groups having 6 to 30 carbon atoms, and alkylaryl groups having 7 to 30 carbon atoms.

[0028] Examples of the linear alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group, and may be a linear alkyl group having 1 to 20 carbon atoms.

[0029] Examples of the branched acyclic alkyl group having 3 to 30 carbon atoms include a branched acyclic alkyl group having 3 to 20 carbon atoms, such as an i-propyl group, an i-butyl group, a t-butyl group, an s-butyl group, an i-pentyl group (3-methylbutyl group), a t-pentyl group (1,1-dimethylpropyl group), an s-pentyl group (1-methylbutyl group), a 2-methylbutyl group, a neopentyl group (2,2-dimethylpropyl group), a 1,2-dimethylpropyl group, an i-hexyl group (4-methylpentyl group), and a 2-heptyl group, and may be a branched acyclic alkyl group having 3 to 8 carbon atoms.

[0030] Examples of the cycloalkyl group having 3 to 30 carbon atoms and optionally having a side chain include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group (bicyclo[4,4,0]decyl group), a 5-tricyclo[3.3.1.13,7]dec-1-yl group (1-adamantyl group), a 5-methyl-2-(propan-2-yl)cyclohexyl group (menthyl group), and a bicyclo-[2.2.1]-hept-2-yl group. The cycloalkyl group may have a side chain having 3 to 20 carbon atoms, or may have a side chain having 3 to 6 carbon atoms.

[0031] Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, a phenethyl group (2-phenylethyl group), a 9-fluorenyl group, a naphthylmethyl group, and a 1-tetralinyl group. The arylalkyl group may be an arylalkyl group having 7 to 15 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms.

[0032] 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 having 3 to 30 carbon atoms and optionally having a side chain include a cyclopentenyl group, a cyclohexenyl group, and a bicyclo[2.2.1]hept-5-en-2-yl group. The cycloalkenyl group may have a side chain having 3 to 10 carbon atoms, or may have a side chain having 5 to 7 carbon atoms.

[0033] Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, an azulenyl group, a biphenyl group, an anthracenyl group, a terphenyl group, a phenanthrenyl group, a triphenylenyl group, a chrysenyl group, a pyrenyl group, and a tetracenyl group. The aryl group may have 6 to 18 carbon atoms, or may have 6 to 12 carbon atoms.

[0034] 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, and examples thereof include alkylaryl groups 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 on the aryl group having 6 to 18 carbon atoms, and may be 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 on 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 a tolyl group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group, and a dodecylphenyl group.

[0035] 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 the heteroatom-containing substituents listed in (iv) below. Examples of the "group containing a heteroatom" include an alkoxy group (OR 11 ), ester group (COR 11 ) and others. 11 is as stated above.

[0036] In (iii) above, R1 , R 2 , R 3 or R 4 The total number of carbon atoms of the substituents corresponding to the above 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 an atom or group selected from the group consisting of heteroatoms and groups containing a heteroatom" refers to (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic 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) each of the groups in (iii-A) above being substituted with one or more of the heteroatoms, (iii-C) each of the groups in (iii-A) above being substituted with one or more of the "groups containing a heteroatom", and (iii-D) each of the groups in (iii-A) above being substituted with one or more of the heteroatoms and 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, and an aryl group substituted with an ester group.

[0037] (iv) The heteroatom-containing substituent is specifically, OR 11 , CO2R 11 , CO2M', C(O)N(R 12 )2, C(O)R 11 , O.C.(O)R 11 , S.R. 11 , SO2R 11 , OSO2R 11 , P(O)(OR 11 ) 2-y (R 11 ) y , C.N., N.R. 11 (R 12 ), Si(OR 12 )3-x (R 12 ) x , OSi(OR 12 ) 3-x (R 12 ) x , NO2, SO3M', PO3M'2, P(O)(OR 12 )2M', or an epoxy-containing group. R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 11 and R 12 If there are multiple R 11 and R 12 and may be the same or different. 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. R 11 and R 12 The number of carbon atoms in the hydrocarbon group 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 from 0 to 3; and y represents an integer from 0 to 2.

[0038] R 1 , R 2 , R 3 and R 4are each independently preferably (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, an anthracenyl group, or an adamantyl 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 ones include (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 a pentafluorophenyl group; and (iv) a methoxy group, a trimethylsilyl group, a trimethylsilyloxy group, and a cyclohexylamino group. R 1 , R 2 , R 3 and R 4 are each independently more preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, a pentafluorophenyl group, a methyl acetate group, a phenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, a 2,6-dicyclohexylphenyl group, a 2,6-diphenylphenyl group (a terphenyl group), a 2,6-diethoxyphenyl group, or a trimethylsilyl group.

[0039] Also, R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring. That is, R 1 , R 2 , R 3 and R 4Adjacent substituents may be linked to each other 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).

[0040] R 5 and R 6 each independently represents (v) 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; (vi) NR 11 (R 12 ), or SiR 11 (R 12 )2 (where R 12 may be the same or different. R 5 and R 6 In the above, the hydrocarbon group having 1 to 30 carbon atoms may be the same as that explained in the above (iii). R 5 and R 6 The heteroatom and the group containing a heteroatom used in may be the same as those explained in the above (iii). R 5 and R 6 In the above formula, the hydrocarbon group having 1 to 30 carbon atoms may be an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. R 5 and R 6 In the above, the alkyl group having 1 to 30 carbon atoms may be a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain. The linear alkyl group having 1 to 30 carbon atoms, the branched acyclic alkyl group having 3 to 30 carbon atoms, the cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, the arylalkyl group having 7 to 30 carbon atoms, and the aryl group having 6 to 30 carbon atoms are included in the above (iii) and may be the same as those explained in the above (iii). R 5 and R 6 In the above formula, the hydrocarbon group having 1 to 30 carbon atoms may be a branched non-cyclic alkyl group having 3 to 20 carbon atoms, a cycloalkyl group which may have a side chain having 3 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 5 and R 6 (vi) NR in 11 (R 12 ), or SiR 11 (R 12 )2 is included in (iv) above and may be the same as that described in (iv) above. R 5 and R 6 may be, among others, a t-butyl group, a menthyl group, an adamantyl group, a phenyl group, a 2,6-dimethoxyphenyl group, a dimethylamino group, or a trimethylsilyl group.

[0041] R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. R 7 The heteroatom used in may be the same as that explained in (iv) above. R 7 The hydrocarbon group having 1 to 20 carbon atoms in the above formula (iii) may be any hydrocarbon group having 1 to 30 carbon atoms that satisfies the condition of having 1 to 20 carbon atoms. R 7 may be, among others, a methyl group, a phenyl group, or a 4-fluorophenyl group. In the general formula [1], R 7 X 1 In the present invention, the metal complex is arranged in the trans position of R 7 and L 1is not limited to the compound having the structure shown in the general formula [1], but also includes compounds having the structure shown in the general formula [1] 7 and L 1 are interchanged, that is, R 7 But X 1 The formula [1-1] and the formula [1-2] below also include compounds having a structure in which R 7 and L 1 The position of is the same as above.

[0042] E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. 1 is preferably a phosphorus atom in terms of its coordination power to metals. X 1 represents an oxygen atom or a sulfur atom. 1 is preferably an oxygen atom in terms of acidity for deprotonation. M represents nickel or palladium.

[0043] L 1 is an auxiliary ligand and represents a compound represented by the general formula [2]. R 8 , R 9 and R 10 are each independently N(R 11 )2 (where R 11 may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. 11 has the same definition as above, except that R 8 , R 9 and R 10 If any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. 8 , R 9 and R 10 may be bonded to each other to form an alicyclic structure.

[0044] R 8 , R 9 and R 10 In the above, the alkyl group having 1 to 20 carbon atoms may be a linear alkyl group having 1 to 20 carbon atoms, a branched non-cyclic alkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain. R 8 , R 9 and R 10 In the formula (iii), the linear alkyl group having 1 to 20 carbon atoms, the branched acyclic alkyl group having 3 to 20 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, the arylalkyl group having 7 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may each be any of those described in the above (iii) that satisfy the condition of having 1 to 20 carbon atoms.

[0045] R 8 , R 9 and R 10 are each independently N(R 11 )2 (where R 11 may be the same or different.) and an oxygen atom, and may be an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms. However, R 8 , R 9 and R 10 When any two of the above are aryl groups having 6 to 12 carbon atoms, the remaining one cannot be an aryl group having 6 to 12 carbon atoms. R 8 , R 9 and R 10 In the above, the alkyl group having 1 to 12 carbon atoms may be a linear alkyl group having 1 to 12 carbon atoms, a branched acyclic alkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain. R 8 , R 9 and R 10In the formula (iii), the linear alkyl group having 1 to 12 carbon atoms, the branched acyclic alkyl group having 3 to 12 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, the arylalkyl group having 7 to 12 carbon atoms, and the aryl group having 6 to 12 carbon atoms may each be any of those described in (iii) above that satisfy the condition of having 1 to 12 carbon atoms.

[0046] The total number of nitrogen atoms contained in the compound represented by the general formula [2] may be 3 or less.

[0047] Specific combinations of substituents and the like in the general formulae [1] and [2] in the present invention are shown in the following Table 1. However, the specific examples are not limited to the following examples. Also included are compounds in which the central metal M of the metal complexes exemplified in Table 1 is changed from Ni to Pd. No. 7 in Table 1 is complex B-1, which will be described later.

[0048] [Table 1]

[0049] The metal complex is represented by R 2 and R 3 may be bonded to each other to form a ring, as represented by the general formula [1-1].

[0050] [ka]

[0051] Specific combinations of substituents in the general formulae [1-1] and [2] according to the present invention are shown in Table 2. However, the specific examples are not limited to the following examples. Also exemplified are compounds in which the central metal M of the metal complexes exemplified in Table 2 is changed from Ni to Pd. Note that No. 37 in Table 2 is complex A-1, which will be described later, and No. 38 is complex C-1, which will be described later.

[0052] [Table 2]

[0053] The metal complex is represented by R 1 and R 2 may be bonded to each other to form a ring, as represented by the general formula [1-2].

[0054] [ka]

[0055] Specific combinations of substituents in the general formulae [1-2] and [2] according to the present invention are shown in Table 3. However, the specific examples are not limited to the following examples. Further, compounds in which the central metal M of the metal complexes exemplified in Table 3 is changed from Ni to Pd are also exemplified.

[0056] [Table 3]

[0057] Specific combinations or structures of the substituents and the like in the general formula [2] in the present invention are shown in the following Table 4. However, the specific examples are not limited to the following examples.

[0058] [Table 4]

[0059] The metal complex of the present invention can be obtained, for example, by contacting a specific ligand with a transition metal compound containing nickel or palladium. The transition metal compound is a compound represented by the general formula [2] (L 1 ) or may not be included. In the latter case, the L 1 Or the above L 1or contacting the specific ligand with the transition metal compound in the presence of a compound or mixture containing 1 Or the above L 1 The metal complex of the present invention can be obtained by contacting a compound or mixture containing the above-mentioned ligand with the metal complex. The above-mentioned specific ligand can be synthesized based on a known synthesis method. 1 A transition metal compound containing L 1 Or the above L 1 The compound or mixture containing L may be commercially available or may be a transition metal compound obtained by the reaction of 1 Or the above L 1 The compound or mixture may include In the present invention, the term "contact" means, for example, bringing a specific ligand and the transition metal compound into sufficient proximity and mixing these compounds. The conditions for mixing the specific ligand 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. The mixing may be carried out in the presence of an olefin. In addition, as described above, the L 1 Or the above L 1 The reaction may be carried out in the presence of a compound or mixture containing the formula [1], or after mixing, a compound represented by the formula [2] may be added. When the obtained metal complex is more thermodynamically stable than the transition metal compound, the reaction proceeds by mixing the specific ligand 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 of the specific ligand and the transition metal compound in order to sufficiently proceed with the reaction. In some cases, the reaction can be promoted by adding an olefin to the mixture. The transition metal compound is 1 In the case where the specific ligand does not contain L, the reaction product of the specific ligand and the transition metal compound is usually 1The metal complex of the present invention can be obtained by introducing L by a ligand exchange reaction. 1 may be introduced by adding 1 equivalent to the transition metal compound, or 2 or more equivalents. The conditions for this reaction are not particularly limited. These compounds may be mixed directly or in a solvent. The reaction may be carried out at room temperature or with heating.

[0060] The metal complex obtained by contacting the specific ligand with a transition metal compound containing nickel or palladium is presumed to have a structure represented by the general formula [1]. However, although the metal complex represented by the general formula [1] is a 1:1 reaction product between the specific ligand and a transition metal compound, it is possible that a reaction product having a different composition ratio may be obtained depending on the type of transition metal compound. For example, it is possible that two or more molecules of the specific ligand form a complex with one transition metal, or that one molecule of the specific ligand 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 metal complexes having structures other than the structure represented by such general formula [1] can be used for producing olefin (co)polymers, similarly to the metal complexes represented by general formula [1].

[0061] [Transition metal compounds] The transition metal compound containing nickel or palladium used in the synthesis of the metal complex of the present invention is one that can react with the specific ligand used in the synthesis of the metal complex of the present invention to form a complex having a polymerizable ability. These are sometimes called precursors.

[0062] Among the transition metal compounds used, examples of transition metal compounds containing nickel atoms include bis(1,5-cyclooctadiene)nickel(0) (hereinafter, may be referred to as Ni(COD)2), (N,N,N,N-tetramethylethylenediamine)nickeldimethyl(II) (hereinafter, (TMEDA)NiMe2) (hereinafter, TMEDA stands for tetramethylethylenediamine), diacetylacetonenickel(II) (hereinafter, Ni(acac)2) (hereinafter, acac stands for acetylacetone), bis(cyclopentadienyl)nickel(II), NiPhCl(PEt3)2 (hereinafter, Ph stands for phenyl, Et stands for ethyl), and NiPhCl(PPh3). 2、 Examples of preferred transition metal compounds include NiPhCl(TMEDA), NiArBr(TMEDA) (wherein Ar represents, for example, 4-fluorophenyl or 4-biphenyl), Ni(CH2CHCH2)2, Ni(CH2CMeCH2)2, Ni(CH2SiMe3)2(pyridine)2 (hereinafter, Py represents pyridine), Ni(CH2SiMe3)2(2,6-lutidine)2 (hereinafter, Lut represents 2,6-lutidine), NiPh2(Py)2, and NiPh2(Lut)2. Examples of preferred transition metal compounds containing palladium atoms include Pd(dibenzylideneacetone)2 (hereinafter, Pd(dba)2) (hereinafter, dba represents dibenzylideneacetone), Pd2(dba)3, Pd3(dba)4, Pd(OCOCH3)2, and (1,5-cyclooctadiene)Pd(methyl)(chloride).

[0063] The metal complex of the present invention can be obtained by contacting a specific ligand with the above-mentioned transition metal compound, for example, in a molar ratio of specific ligand:transition metal compound=1:99 to 99:1, in an organic solvent such as toluene or benzene at 0 to 100° C. under reduced pressure to pressure for 1 to 86,400 seconds.

[0064] After this reaction, a part of the components constituting the transition metal compound other than the transition metal in the compound is replaced by a specific ligand, and a metal complex is generated as a reaction product between the specific ligand and the transition metal compound. This replacement reaction preferably proceeds quantitatively, but in some cases it does not have to proceed completely. After the reaction is completed, in addition to the metal complex of the present invention, the specific ligand and other components derived from 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.

[0065] 2. Olefin polymerization catalyst components The olefin polymerization catalyst component 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 polymerization or copolymerization of olefins. As described above, the metal complex of the present invention can be produced by reacting a specific ligand with a transition metal compound containing a compound represented by general formula [2], or by contacting a product obtained by contacting a specific ligand with a transition metal compound with a compound represented by general formula [2]. In the latter case, the three components may be contacted simultaneously, or the product may be contacted with a compound represented by general formula [2]. When the metal complex of the present invention is used as a catalyst component, the reaction solution may be used as it is, an isolated product may be used, or a product supported on a carrier may be used. Supporting on a carrier may be performed in a reactor used for polymerization of olefins or copolymerization of olefins with comonomers such as (meth)acrylic acid esters, in the presence or absence of these monomers, or in a vessel separate from the reactor.

[0066] 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, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc. or mixtures thereof can be mentioned, and mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, and SiO2-Cr2O3 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.

[0067] 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, anoxicite, 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.

[0068] 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. Shape control such as pulverization or granulation, or drying treatment may be performed.

[0069] 3. Olefin polymerization catalysts The olefin polymerization catalyst of the present invention is characterized by comprising the following components (A) and, optionally, (B): Component (A): The metal complex of the present invention Component (B): Organoaluminum compound

[0070] Component (A) is the metal complex of the present invention, and one type of metal complex may be used alone, or two or more types of metal complexes may be used in combination.

[0071] An example of an organoaluminum compound used as component (B) is represented by the following general formula: Al(R p ) a X (3-a) In the general formula, R p represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group, and a represents a number greater than 0 and equal to or less than 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.

[0072] Among these, triisobutylaluminum or tri-n-octylaluminum is preferred. Two or more of the above-mentioned organoaluminum compounds may be used in combination. The above-mentioned 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, and preferred specific examples are 2,6-dimethylphenol and 2,6-di-t-butylphenol.

[0073] 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. In each component, different kinds of components may be used as a mixture. 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-mentioned 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, or in a monomer such as an olefin using a solution of the above-mentioned component (A) in the inert hydrocarbon solvent. 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.

[0074] 4. Method for producing olefin polymer One embodiment of the process for producing an olefin polymer of the present invention is to polymerize or copolymerize an olefin in the presence of the above-mentioned catalyst component for olefin polymerization or catalyst for olefin polymerization of the present invention. The olefin in the present invention has the general formula: CH2=CHR 20 where R 20 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 20 If the carbon number of R is more than 20, sufficient polymerization activity tends not to be exhibited. 20 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. More preferred olefins include ethylene, propylene, α-olefins such as 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 multiple olefins may be used in combination. In the process for producing an olefin polymer and the process for producing an olefin copolymer of the present invention, the olefin is preferably an olefin having 3 to 20 carbon atoms, and particularly preferably propylene.

[0075] Another embodiment of the method for producing an olefin polymer of the present invention comprises copolymerizing (a) an olefin with (b) a (meth)acrylic acid ester monomer, a vinyl monomer or an allyl monomer in the presence of the above-mentioned olefin polymerization catalyst component or olefin polymerization catalyst.

[0076] The (meth)acrylic acid ester monomer in the present invention is represented by the general formula: CH2=C(R 21 )CO2(R 22 ), where R 21 R is a hydrogen atom or a methyl group. 22 is a hydrocarbon group having 1 to 30 carbon atoms, which may have a branch, a ring, and / or an unsaturated bond. 22 It may contain a heteroatom at any position within the group. R 22 If the carbon number of R exceeds 30, the polymerization activity tends to decrease. 22 The number of carbon atoms in R is 1 to 30. 22 preferably has 1 to 12 carbon atoms, and more preferably has 1 to 8 carbon atoms. Also, R 22 Examples of the heteroatom that may be contained within R include an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen atom, a silicon atom, a fluorine atom, and a boron atom. Among these heteroatoms, an oxygen atom, a silicon atom, and a fluorine atom are preferred, and an oxygen atom is more preferred. 22 It is also preferred that the group does not contain a heteroatom.

[0077] 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. In addition, a single (meth)acrylic acid ester may be used, or multiple (meth)acrylic acid esters may be used in combination.

[0078] 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 carboxyl group, a formyl group, an ester group, an epoxy group, a nitrile group, or the like. 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.

[0079] 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 of an atom containing a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc., and is particularly a vinyl monomer containing a halogen atom, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a formyl group, an ester group, an epoxy group, a nitrile group, etc. Preferred specific examples include allyl acetate, allyl alcohol, allylamine, N-allylaniline, Nt-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.

[0080] The polymerization reaction of the present invention is carried out in the presence or absence of a liquid such as a hydrocarbon solvent, such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, or a liquid 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, or acetonitrile. A mixture of the liquid compounds described herein may also be used as a solvent. Furthermore, an ionic liquid may also be used as a solvent. In order to obtain a high polymerization activity and a high molecular weight, the above-mentioned hydrocarbon solvents and ionic liquids are more preferable.

[0081] 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 alkoxide of tetravalent titanium and BHT, etc. can be used. In addition, inorganic and / or organic fillers can be used as additives, and polymerization can be carried out in the presence of these fillers. Furthermore, the auxiliary ligand L according to the present invention can be used in the presence of the additives. 1 or an ionic liquid may be used as an additive.

[0082] The amount of the additive is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, more preferably 0.3 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 additive to the polymerization system, and any method can be used. For example, the additive may be added by mixing with the olefin polymerization catalyst component of the present invention, or may be added by mixing with a monomer, or may be added to the polymerization system independently of the olefin polymerization catalyst component or the monomer. In addition, a plurality of additives may be used in combination. In addition, the auxiliary ligand L according to the present invention may be used in combination with the auxiliary ligand L according to the present invention. 1The compound may be the same as or different from the compound described above.

[0083] 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 ion 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 types may be used.

[0084] The unreacted monomers and the medium may be separated from the resulting copolymer and recycled. In recycling, these monomers and media may be reused after purification or without purification. The resulting copolymer can be separated from the unreacted monomers and media by a conventional method. 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, and preferably 0°C to 250°C, the copolymerization pressure from 0.1 MPa to 300 MPa, and preferably 0.3 MPa to 250 MPa, and the polymerization time from the ranges of 0.1 minute to 10 hours, and preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

[0085] 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.

[0086] 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.

[0087] In particular, the copolymer with the polar group-containing monomer obtained by the present invention exhibits good coating properties, 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. By utilizing these properties, the copolymer of the present invention can be used in various applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizer, wax, etc. EXAMPLES

[0088] 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 used were dehydrated and deoxygenated. The abbreviations used in the following synthesis examples are as follows. EtOAc: ethyl acetate CDM: Dichloromethane OAc: Acetate (-OC(O)CH3) OMOM: Methoxymethoxy (-OCH2OCH3) MOM: Methoxymethyl (-CH2OCH3) THF: tetrahydrofuran Ad: Adamantil Py: Pyridine, pyridyl BI-DIME: 3-(tert-butyl)-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]oxaphosphore dba: dibenzylideneacetone DPEPhos: Bis[2-(diphenylphosphino)phenyl]ether

[0089] 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 10 mg) was collected in a vial for the high-temperature GPC pretreatment device PL-SP 260VS manufactured by Polymer Laboratory Co., Ltd., and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L) was added to adjust the polymer concentration to 0.05 (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 in the present invention, no polymer was captured by the glass filter. Next, GPC measurement was performed using a column manufactured by Tosoh Corporation TSKgel GMH6-HT (30 cm × 4 columns) and a Tosoh Corporation 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.

[0090] (2) Structure assignment by NMR The assignment of the ligand structure was carried out using an NMR measurement device (Bruker's "Ascend 400") according to the following procedure. The ligand was dissolved in a deuterated solvent, and measurements were performed at 25°C for 16 cumulative measurements.

[0091] 2. Synthesis of the ligand (Synthesis Example 1): Synthesis of Ligand A Ligand A was synthesized according to the following scheme.

[0092] [ka]

[0093] (i) Synthesis of Compound 2 To a solution of compound 1 (20 g, 89.6 mmol) in THF (150 mL), NaH (7.17 g, 179.3 mmol) was slowly added at 0 ° C. After stirring at 20 ° C for 1 hour, MOMCl (12.0 g, 149.4 mmol) was slowly added at 0 ° C. and stirred at 20 ° C for 16 hours to obtain a gray suspension solution. An aqueous solution of NaHCO3 (300 mL) was added, and extraction was performed with ethyl acetate (350 mL × 3). The collected organic layer was washed with water (300 mL × 2) and brine (150 mL), dried over Na2SO4, filtered, and the residual solvent was distilled off under reduced pressure. Compound 2 (17.1 g, 64.0 mmol, 71% yield) was obtained as a yellow oil by silica gel column chromatography.

[0094] (ii) Synthesis of Compound 4 To a solution of compound 3 (10 g, 41.4 mmol) in THF (50 mL), n-BuLi (2.5 M, 18.2 mL, 1.1 equivalents) was slowly added at -78 ° C. After stirring for 2 hours at -78 ° C, B(OMe)3 (9.48 g, 91.2 mmol) was slowly added at -78 ° C., and the mixture was stirred at 20 ° C. for 12 hours to obtain a yellow suspension. HCl (1 M) was slowly added until the pH became 6-7, and the mixture was washed with water (50 mL), extracted with ethyl acetate (100 mL × 3), washed with brine (150 mL), dried over Na2SO4, filtered, and the solvent was distilled off under reduced pressure. The resulting yellow oil compound 4 was used as it was in the next reaction.

[0095] (iii) Synthesis of Compound 5 Compound 4 (7.5 g, 28.0 mmol), compound 2 (8.68 g, 42.1 mmol), t-BuONa (8.1 g, 84.2 mmol), Pd(OAc)2 (63.0 mg, 0.280 mmol), and BI-DIME (185.5 mg, 0.561 mmol) were dissolved in toluene (30 mL). The reaction solution was purged with nitrogen three times and heated at 110 ° C for 30 hours to obtain a black suspension. The reaction solution was cooled to 25 ° C, filtered, washed with dichloromethane (25 mL × 3), and the residual solvent was distilled off under reduced pressure. Compound 5 (5.16 g, 14.8 mmol, yield 52%) was obtained as a white solid by silica gel column chromatography.

[0096] (iv) Synthesis of Compound 6 To a solution of compound 5 (8.8 g, 25.2 mmol) in THF (35 mL), n-BuLi (2.5 M, 11.1 mL, 1.1 equivalents) was added at -78 °C. After stirring at 20 °C for 3 hours, a solution of I2 (9.61 g, 37.8 mmol) in THF (9 mL) was added at -78 °C, and the mixture was stirred at 20 °C for 12 hours to obtain a yellow suspension. Water (100 mL) was added, and the mixture was extracted with ethyl acetate (150 mL x 3), washed with aqueous NaHCO3 solution (100 mL) and brine (100 mL), dried over Na2SO4, filtered, and the solvent was distilled off under reduced pressure. Compound 6 (5.75 g, 12.1 mmol, 48% yield) was obtained as a white solid by silica gel column chromatography.

[0097] (v) Synthesis of compound 7 Compound 6 (200 mg, 0.421 mmol), Pd2(dba)3 (11.5 mg, 0.0126 mmol), DPEPhos (4.54 mg, 0.00843 mmol), Cs2CO3 (274.7 mg, 0.843 mmol), t-Bu2PH (73.9 mg, 0.505 mmol) were dissolved in toluene (1.5 mL) and nitrogen substitution was performed three times. The mixture was stirred at 110 ° C for 13 hours to obtain a skin-colored suspension. The reaction solution was cooled to 25 ° C, filtered, and washed with dichloromethane (25 mL × 3). The collected organic layer was distilled under reduced pressure. Compound 7 (0.10 g, 0.202 mmol, yield 48%) was obtained as a yellow solid by silica gel column chromatography.

[0098] (vi) Synthesis of compound 8 BH3-Me2S (10M, 1.06mL, 2eq) was added dropwise to a solution of compound 7 (2.6g, 5.28mmol) in THF (20mL) at 0°C, and the mixture was stirred at 20°C for 1 hour to obtain a yellow suspension. The reaction solution was carefully quenched with water (50mL), extracted with ethyl acetate (80mL), and the collected organic layer was washed with brine (80mL), dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. Hexane was added at 20°C to isolate compound 8 (2.0g, 3.95mmol, 74% yield) as a white solid.

[0099] (vii) Synthesis of Ligand A To a solution of compound 8 (10 g, 19.7 mol) in dichloromethane (40 mL), HCl / ethyl acetate (10 M, 40 mL, 20.2 equivalents) was added dropwise at 0°C and stirred at 20°C for 3 hours to obtain a yellow solution. Aqueous NaHCO3 solution (100 mL) was added and extracted with ethyl acetate (100 mL). The organic layer was washed with brine (100 mL), dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. Ligand A (8.1 g, 18.0 mmol, 91% yield) was obtained as a yellow solid by recrystallization. 1 H NMR (400MHz, CDCl3,δ,ppm):0.97(d,6H),1.06(d,6H),1.30(s,9H),1.33(s,9H),2.41 (m,2H),7.23(m,1H),7.32(m,4H),7.45(m,1H),7.83(m,1H),8.00(m,1H),8.21(m,1H). 31 P NMR (162MHz, CDCl3,δ,ppm):-4.64(s).

[0100] (Synthesis Example 2): Synthesis of Ligand B The following ligand B was synthesized according to the following scheme.

[0101] [ka]

[0102] (i) Synthesis of compound 10 Synthesized according to Patent No. 6913051. (ii) Synthesis of compound 11 Synthesized according to Patent No. 6913051. (iii) Synthesis of compound 12 Compound 11 (6.31 g, 21.1 mmol) was added dropwise to a solution of THF (40 ml) at 0° C., and the mixture was heated to 30° C. and stirred for 2 hours. CuCl (2.30 g, 23.3 mmol) was added to this suspension at 0° C., and the mixture was heated to 30° C. and stirred for 1 hour. The reaction solution was cooled to −78° C., and t-Bu2PCl (3.82 g, 21.1 mmol) was slowly added and 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 with a silica gel column to obtain a pink solid. DCM 80 ml and ammonia water 100 ml were added to this pink solid, and the mixture was stirred at 30° C. for 1 hour. The organic layer obtained after the liquid separation operation was concentrated to obtain a crude product. This was purified using a silica gel column (developing solvent: petroleum ether (PE): EtOAc: DCM = 50:1:1) to obtain 2.40 g of compound 12. (iv) Synthesis of Ligand B A solution of hydrochloric acid / EtOAc (4M, 80ml) was added to a solution of compound 12 (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 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 B. 1 H NMR (400MHz, 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 (162MHz, CDCl3,δ,ppm):-5.48(s).

[0103] (Synthesis Example 3): Synthesis of Ligand C Ligand C was synthesized according to the following scheme.

[0104] [ka]

[0105] (i) Synthesis of compound 14 To a solution of compound 13 (5.0 g, 22.4 mmol) in THF (100 mL), NaH (1.43 g, 35.8 mmol) was added at 0°C. After stirring at 20°C for 1 h, a gray suspension was obtained. MOMBr (5.60 g, 44.8 mmol) was slowly added at 0°C and stirred at 20°C for 12 h to obtain a yellow suspension. After quenching the reaction in an ice bath (200 mL), extraction was performed with ethyl acetate (200 mL x 3), dried over Na2SO4, filtered, and the residual solvent was distilled off under reduced pressure to obtain a yellow oil. Compound 14 (5.6 g, 20.9 mmol, 93% yield) was obtained as a yellow oil by silica gel column chromatography.

[0106] (ii) Synthesis of compound 15 Compound 14 (1.0 g, 3.74 mmol), Pd2(dba)3 (102.8 mg, 112.3 mmol), DPEPhos (120.9 mg, 0.224 mmol), Cs2CO3 (2.44 g, 7.49 mmol), and t-Bu2PH (1.09 g, 7.49 mmol) were dissolved in dioxane (20 mL) and stirred at 100 °C for 12 hours to obtain a yellow suspension. The remaining solvent was removed under reduced pressure to obtain a gray suspension. The resulting gray oil, compound 15 (1.24 g), was used as is in the next reaction.

[0107] (iii) Synthesis of compound 16 To a solution of compound 15 (1.2 g, 3.73 mmol) in dioxane (20 mL), BH3-Me2S (10 M, 1.12 mL, 3 equivalents) was added dropwise at 0°C, and the mixture was stirred at 20°C for 12 hours to obtain a gray suspension. The reaction solution was quenched with water (20 mL), extracted with ethyl acetate (20 mL x 3), dried over Na2SO4, filtered, and the solvent was distilled off under reduced pressure. Compound 16 (1.1 g, 3.18 mmol, 85% yield) was obtained as a white solid by silica gel column chromatography.

[0108] (iv) Synthesis of compound 17 To a solution of compound 16 (3.0 g, 8.6 mmol) in THF (60 mL), n-BuLi (2.5 M, 4.16 mL, 1.2 equivalents) was slowly added at 0° C. The mixture was stirred at 20° C. for 2 hours to obtain a green solution. C6F6 (4.84 g, 25.9 mmol) was added at 0° C., and the mixture was stirred at 20° C. for 12 hours to obtain a yellow solution. The solvent was removed under reduced pressure, and compound 17 (7.5 g) was obtained as a crude yellow solid by silica gel column chromatography, which was used as it was in the next reaction.

[0109] (v) Synthesis of Ligand C Compound 17 (1.4 g, 2.73 mmol) was added with HCl / Dioxane (100 mL) at 0° C. and stirred at 20° C. for 2 hours to obtain a white suspension. The solvent was removed under reduced pressure to obtain a white solid. Extraction was performed with dichloromethane (500 mL), and the organic layer was washed with an aqueous NaHCO3 solution (250 mL×2), dried over Na2SO4, filtered, and the solvent was removed under reduced pressure to obtain Ligand C (1.2 g) as a yellow solid. 1 H NMR (400MHz, CDCl3,δ,ppm):1.25(s,9H),1.30(s,9H),7.31(m,1H),7.37(m,1H),7.46(m,1H),7.84(m,1H),8.26(m,1H),8.35(m,1H). 19 F NMR (376MHz, CDCl3,δ,ppm):-162.7(s,2F),-155.4(s,1F),-138.2(s,2F). 31P NMR:(162MHz, CDCl3,δ,ppm):-5.53(s).

[0110] 3. Polymerization Evaluation (Example 1): Polymerization of propylene using metal complex A-1 (1) Synthesis of metal complex A-1 Metal complex A-1 was synthesized according to the following scheme.

[0111] [ka]

[0112] (i) Synthesis of compound 18 Compound 18 was obtained by synthesis according to the method described in Molecules, 2014, 19, 13603-13613. (ii) Synthesis of metal complex A-1 Ligand A (448 mg, 1.0 mmol) and NaH (48 mg, 2.0 mmol) were dissolved in THF (10 ml) under a nitrogen atmosphere and stirred at room temperature for 30 minutes to obtain a yellow solution. Residual NaH was removed by celite filtration. The obtained solution was mixed with compound 18 (350 mg, 1.0 mmol) obtained in (i) above and stirred at room temperature for 30 minutes. The solvent was distilled off under reduced pressure, and the obtained solid was extracted three times with hexane (20 ml) to obtain an orange solution. The solvent was distilled off under reduced pressure to obtain metal complex A-1 (710 mg, 99% yield) as an orange solid.

[0113] (2) Polymerization of propylene Propylene (500 mL) was introduced into an induction stirring autoclave with an internal volume of 2 L. Metal complex A-1 (0.10 mmol) obtained in (1) above was fed into the autoclave. The autoclave was heated to 50° C. with stirring to initiate polymerization. After polymerization for 1 hour, the remaining propylene was removed to terminate the reaction. The autoclave was then opened to obtain a polymer. The polymerization results are shown in Table 5. The activity represents the polymer yield (kg) per 1 mol of metal complex used in polymerization. The results of GPC for the obtained polymer are also shown in Table 5.

[0114] (Example 2): Polymerization of propylene using metal complex B-1 (1) Synthesis of metal complex B-1 Metal complex B-1 was synthesized according to the following scheme.

[0115] [ka]

[0116] Metal complex B-1 (668 mg, yield 99%) was obtained in the same manner as in Example 1(1), except that ligand B (400 mg, 1.0 mmol) was used instead of ligand A.

[0117] (2) Polymerization of propylene As shown in Table 5, a polymer was obtained in the same manner as in Example 1, except that Metal Complex A-1 was changed to Metal Complex B-1.

[0118] (Example 3): Polymerization of propylene using metal complex C-1 (1) Synthesis of metal complex C-1 Metal complex C-1 was synthesized according to the following scheme.

[0119] [ka]

[0120] Metal complex C-1 (531 mg, yield 73%) was obtained in the same manner as in Example 1(1), except that ligand C (454 mg, 1.0 mmol) was used instead of ligand A.

[0121] (2) Polymerization of propylene As shown in Table 5, a polymer was obtained in the same manner as in Example 1, except that metal complex A-1 was changed to metal complex C-1.

[0122] Comparative Example 1: Polymerization of propylene using metal complex A-2 (1) Synthesis of metal complex A-2 Metal complex A-2 was synthesized according to the following scheme.

[0123] [ka]

[0124] Pyridine (220 mg, 2.8 mmol) was added to a solution of metal complex A-1 (200 mg, 0.28 mmol) in toluene (10 ml), and the mixture was stirred at room temperature for 30 minutes. The solvent was removed under reduced pressure to obtain complex A-2 (185 mg, 98% yield).

[0125] (2) Polymerization of propylene As shown in Table 5, a polymer was obtained in the same manner as in Example 1, except that Metal Complex A-1 was changed to Metal Complex A-2.

[0126] Comparative Example 2: Polymerization of propylene using ligand A (i) Preparation of the catalyst Ni(COD)2 (55.0 mg, 0.20 mmol) was weighed into a two-necked eggplant flask, and toluene (10.0 mL) was added to make a 0.02 mmol / mL solution. 5.00 mL of this 0.02 mmol / mL toluene solution of Ni(COD)2 was added to the two-necked eggplant flask containing Ligand A (64.0 mg, 0.10 mmol) and stirred at room temperature for 30 minutes to obtain a catalyst. (2) Polymerization of propylene A polymer was obtained in the same manner as in Example 1, except that metal complex A-1 was replaced with the catalyst obtained in (i) above (whole amount used) as shown in Table 5. The activity was calculated assuming that the ligand reacted with Ni(COD)2 in a 1:1 ratio to form a nickel complex.

[0127] Comparative Example 3: Polymerization of propylene using ligand B (i) Preparation of the catalyst Except for changing the ligand A to the ligand B, the preparation was carried out in the same manner as in (i) of Comparative Example 2. (2) Polymerization of propylene A polymer was obtained in the same manner as in Example 1, except that metal complex A-1 was replaced with the catalyst obtained in (i) above (whole amount used) as shown in Table 5. The activity was calculated assuming that the ligand reacted with Ni(COD)2 in a 1:1 ratio to form a nickel complex.

[0128] Comparative Example 4: Polymerization of propylene using ligand C (i) Preparation of the catalyst Except for changing the ligand A to the ligand C, the preparation was carried out in the same manner as in (i) of Comparative Example 2. (2) Polymerization of propylene A polymer was obtained in the same manner as in Example 1, except that metal complex A-1 was replaced with the catalyst obtained in (i) above (whole amount used) as shown in Table 5. The activity was calculated assuming that the ligand reacted with Ni(COD)2 in a 1:1 ratio to form a nickel complex.

[0129] [Table 5]

[0130] 4. Discussion As shown in Table 5, the metal complexes of the present invention shown in Examples 1 to 3 were obtained by adding the auxiliary ligand L 1 It was confirmed that, in comparison with a catalyst not containing the compound and the pyridine metal complex shown in Comparative Example 1, this was a highly active olefin polymerization catalyst in olefin polymerization. The TMEDA metal complex using a ligand different from the ligand specified in the present invention, as disclosed in Non-Patent Document 3, shows a maximum 8.9-fold improvement in activity compared to the pyridine metal complex (entry 1 vs. 4 in Table 1). This is the result when the polymerization temperature is 10°C, and when the polymerization temperature is increased to 30°C, the activity is improved by 2.6-fold and the molecular weight is also reduced (entry 3 vs. 6 in Table 1). On the other hand, the metal complex of the present invention was more than 10 times (11.8 times) more active than the pyridine metal complex even at a polymerization temperature of 50°C, and the molecular weight was maintained. Non-Patent Document 4 discloses a TMEDA metal complex formed by combining a ligand different from the ligand specified in the present invention with PdMe2(TMEDA), and the activity is improved by up to about two times compared to a pyridine metal complex (1 vs. 3 in Table 1). Non-Patent Document 4 also shows that there is a tendency for the molecular weight to decrease when a pyridine metal complex is converted to a TMEDA metal complex (2 vs. 4, 8 vs. 10, 9 vs. 11 in Table 1). On the other hand, the metal complex of the present invention was more than 10 times (11.8 times) more active than the pyridine metal complex, and the molecular weight was maintained. Therefore, it was confirmed that the olefin polymerization catalyst is highly active by the combination of a specific ligand structure (particularly the substituent on P) and a specific auxiliary ligand. In addition, in Comparative Example 1, it was confirmed that the molecular weight tends to decrease by the addition of the Lewis base disclosed in Patent Document 1, but as shown in Example 1 and Comparative Example 2, it was confirmed that the molecular weight is maintained in the present invention. [Industrial Applicability]

[0131] By using the metal complex of the present invention, it is possible to produce olefin polymers, particularly propylene polymers, with high activity while maintaining the molecular weight of the polymer, and therefore the metal complex is extremely useful industrially and is of great industrial utility.

Claims

1. A metal complex represented by the following general formula [1]: 【Chemistry 1】 [In formula 1, R １ , R ２ , R ３ and R ４ each independently represents 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 heteroatoms and groups containing heteroatoms; (iv) OR １１ , CO ２ R １１ , CO ２ M', C(O)N(R １２ ) ２ , C(O)R １１ , O.C.(O)R １１ , S.R. １１ , S.O. ２ R １１ , OSO ２ R １１ , P(O)(OR １１ ) ２－ｙ (R １１ ) ｙ , C.N., N.R. １１ (R １２ ), Si(OR １２ ) ３－ｘ (R １２ ) ｘ , OSi(OR １２ ) ３－ｘ (R １２ ) ｘ , NO ２ , S.O. ３ M', P.O. ３ M' ２ , P(O)(OR １２ ) ２ M', or an epoxy-containing group. 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. １１ and R １２ When there are multiple R １１ and R １２ may be the same or different. 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. １ , R ２ , R ３ and R ４ may be bonded to each other to form a ring. R ５ and R ６ each independently represents 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; １１ (R １２ ), or SiR １１ (R １２ ) ２ (Here, two R １２ may be the same or different. R ７ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. E １ represents a phosphorus atom, an arsenic atom, or an antimony atom. X １ represents an oxygen atom or a sulfur atom. M represents nickel or palladium. L １ is an auxiliary ligand and represents a compound represented by the general formula [2]. [In formula [2], R ８ , R ９ and R １０ Each independently represents N(R １１ ) ２ (Here, two R １１ may be the same or different.) and an oxygen atom, an alkyl group having 1 to 20 carbon atoms which may have at least one selected from the group consisting of an aryl group having 7 to 20 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 20 carbon atoms. １１ has the same definition as above. ８ , R ９ and R １０ When any two of R are aryl groups having 6 to 20 carbon atoms, the remaining one cannot be an aryl group having 6 to 20 carbon atoms. ８ , R ９ and R １０ may be bonded to each other to form an alicyclic structure.

2. The R ８ , R ９ and R １０ Each independently represents N(R １１ ) ２ (Here, two R １１ may be the same or different.) and an oxygen atom, an alkyl group having 1 to 12 carbon atoms which may have at least one selected from the group consisting of an arylalkyl group having 7 to 12 carbon atoms which may contain an oxygen atom, or an aryl group having 6 to 12 carbon atoms (provided that R ８ , R ９ and R １０ The metal complex according to claim 1, wherein when any two of the groups are aryl groups having 6 to 12 carbon atoms, the remaining one is not an aryl group having 6 to 12 carbon atoms.

3. The metal complex according to claim 1, wherein the total number of nitrogen atoms contained in the compound represented by the general formula [2] is 3 or less.

4. The R ５ and R ６ each independently represents an alkyl group having 1 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which optionally has at least one selected from the group consisting of a heteroatom and a group containing a heteroatom.

5. The R ５ and R ６ are each independently a branched acyclic alkyl group having 3 to 20 carbon atoms which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom, a cycloalkyl group having 3 to 20 carbon atoms which may have a side chain, or an aryl group having 6 to 15 carbon atoms, which may have at least one selected from the group consisting of heteroatoms and groups containing a heteroatom.

6. A catalyst component for olefin polymerization, comprising the metal complex according to any one of claims 1 to 5.

7. An olefin polymerization catalyst comprising the metal complex according to any one of claims 1 to 5.

8. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin having 3 to 20 carbon atoms in the presence of the catalyst component for olefin polymerization according to claim 6.

9. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to claim 7.

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