Metal complex, catalyst component for olefin polymerization containing said metal complex, catalyst for olefin polymerization, and method for producing olefin polymer using said catalyst for olefin polymerization

Abstract

To provide a novel metal complex that can yield a high-molecular-weight polypropylene polymer with high activity.SOLUTION: A metal complex is a product from a reaction between a compound represented by the following formula [I] or [II] with a transition metal compound comprising a transition metal belonging to Group 9, 10 or 11 in the periodic table. R5 and R6 independently represent an optionally substituted fused polycyclic hydrocarbon group. E1 is a phosphorus atom, an arsenic atom or an antimony atom. X1 is an oxygen atom, a sulfur atom or SO3. In formula [I], Z is a hydrogen atom or a leaving group, m is a valence of Z.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a metal complex useful for producing olefin polymers and copolymers, an olefin polymerization catalyst component and an olefin polymerization catalyst using the metal complex, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Background technology]

[0002] Copolymers of olefins and polar group-containing monomers are industrially useful polymers. To obtain these copolymers by direct polymerization, the high-pressure radical method is usually used. However, this method has the drawback of not being able to polymerize propylene or higher α-olefins. It is industrially difficult to obtain copolymers using methods other than high-pressure radical methods, and when using Ziegler catalysts or metallocene catalysts, catalyst deactivation is unavoidable.

[0003] Subsequently, the copolymerization of ethylene and methyl methacrylate became possible using organo rare earth metal complex metallocene catalysts, and since the 1990s, the copolymerization of ethylene and polar group-containing comonomers using late transition metal complex catalysts has been intensively studied. For example, the (α-diimine)palladium complex reported by Brookhart et al. (see Non-Patent Document 1) and the (salicylamidinate)nickel catalyst reported by Grubbs et al. (see Non-Patent Document 2) are known. When using these catalysts, the polymerization temperature is lowered to suppress frequent chain transfer, which generally results in low copolymer productivity and low molecular weight.

[0004] In recent years, the above-mentioned problems in the copolymerization of ethylene with a polar group-containing monomer have been overcome with the discovery of (phosphorus sulfonate)palladium complexes (see Patent Document 1) and (phosphorus phenolate)nickel complexes (see Patent Documents 2, 3 and 4, and Non-Patent Documents 3 and 4), which are nickel catalysts having ligands with phosphorus and oxygen as coordinating atoms and are known as SHOP catalysts. Thus, (phosphorus phenolate) nickel complexes were useful as copolymerization catalysts for ethylene and polar group-containing monomers. However, there was still room for improvement in terms of activity and molecular weight for olefin polymerization, particularly propylene polymerization, and copolymerization of propylene with polar group-containing monomers.

[0005] Also disclosed is a catalyst that combines a phosphinosulfonic acid ligand having a fluorenyl group on the phosphorus with a palladium(0) compound (see Patent Documents 5 and 6). Although this palladium complex has also been shown to be useful as a copolymerization catalyst for ethylene and a polar group-containing monomer, it has not been disclosed that propylene polymerization or copolymerization of propylene and a polar group-containing monomer proceeds, and there is still room for improvement from the viewpoint of achieving high molecular weight in olefin polymerization, particularly propylene polymerization. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-150246 [Patent Document 2] International Publication No. 2010 / 050256 [Patent Document 3] U.S. Patent No. 6,559,326 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-307021 [Patent Document 5] International Publication No. 2020 / 175482 [Patent Document 6] Japanese Patent Publication No. 2020-164828 [Non-patent literature]

[0007] [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] J. Heinicke et al., "Chem. Eur. J.", 2003, 9, 6093-6107. [Non-patent document 4] J. Heinicke et al., "European Journal of Inorganic Chemistry", 2000, 3, 431-440. Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a novel metal complex or catalyst component which can be used in the production of olefins, particularly propylene polymers and copolymers, and which can give polymers with high activity and higher molecular weights, as well as a method for producing olefins, particularly propylene polymers and copolymers, using the same. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the present inventors have found that a compound represented by general formula [I] or [II], which is capable of reacting with a transition metal, 1 X having two condensed polycyclic hydrocarbon groups on it and capable of reacting with transition metals 1 Ortho position (R 1 When a novel metal complex, which is a reaction product of a ligand having a specific substituent on the olefin group and a transition metal compound of Groups 9 to 11 of the periodic table, is used as a catalyst component, olefin polymerization, especially propylene polymerization, proceeds with high activity, resulting in E 1 The present inventors have found that the molecular weight is significantly improved compared to a ligand having one fused polycyclic hydrocarbon group on the cation, and have completed the present invention.

[0010] That is, one embodiment of the present invention provides a metal complex that is a reaction product of a compound represented by the following general formula [I] or [II] and a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table:

[0011] [ka] [R in formula [I] and [II] 1 ~R 6 , E 1 , and X 1 is as follows: R 1 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms. 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 atoms (iii) A linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of heteroatoms and groups containing heteroatoms. (iv) OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 9 ) 2-y(R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 8 )2M', or an epoxy-containing group, where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. R 2 , R 3 and R 4 Adjacent 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 an oxygen atom, a nitrogen atom, and a sulfur atom, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. R 5 or R 6 each independently represents a fused polycyclic hydrocarbon group which may have a substituent. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom, a sulfur atom, or SO3. In addition, in the general formula [I], Z represents a hydrogen atom or a leaving group; m represents the valence of Z.]

[0012] One embodiment of the present invention provides a metal complex represented by the following general formula [III]:

[0013] [ka] [In general formula [III], R 1 ~R 6 , E 1 , and X 1 is the same as above. M represents a transition metal atom belonging to Group 9, 10 or 11 of the periodic table. R 7 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L 1 represents a ligand coordinated to M. R 7 and L 1 may be bonded to each other to form a ring.

[0014] Another embodiment of the present invention provides a catalyst component for olefin polymerization, comprising the metal complex of the present invention.

[0015] Another embodiment of the present invention provides an olefin polymerization catalyst comprising the olefin polymerization catalyst component of the present invention.

[0016] Another embodiment of the present invention provides an olefin polymerization catalyst comprising a reaction product of a compound represented by the following general formula [I] or [II] and a transition metal compound containing a transition metal belonging to Group 9, 10 or 11 of the periodic table:

[0017] [ka] [R in formula [I] and [II] 1 ~R 6 , E 1 , and X 1 is the same as above. In addition, Z and m in the general formula [I] are the same as those defined above.

[0018] In the metal complex, olefin polymerization catalyst component, and olefin polymerization catalyst of the present invention, the transition metal compound may contain a transition metal belonging to Group 10 of the periodic table, in order to provide a polymer with high activity and high molecular weight.

[0019] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, R 5 or R 6 may each independently be a fused polycyclic hydrocarbon group formed by condensing three or more rings which may have a substituent.

[0020] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, R 5 or R 6 may each independently be a fluorenyl group or a 9,10-dihydroanthracenyl group, each of which may have a substituent.

[0021] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, R 1 may be an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms.

[0022] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, R 1 may be a substituent represented by the following general formula (1).

[0023] [ka] (In the general formula (1), R a each independently represents a linear or branched acyclic alkyl group having two or more carbon atoms; R b each independently represents a hydrogen atom or a linear or branched acyclic alkyl group, and * represents a bond.

[0024] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, R 1may be a 2,6-diisopropylphenyl group.

[0025] In the metal complex, olefin polymerization catalyst component, and olefin polymerization catalyst of the present invention, the transition metal compound may contain a nickel atom or a palladium atom, in order to provide a polymer with high activity and a high molecular weight.

[0026] In the metal complex, the catalyst component for olefin polymerization, and the catalyst for olefin polymerization of the present invention, E 1 may be a phosphorus atom. In addition, in the metal complex of the present invention, X is preferably used in order to give a polymer having high activity and a high molecular weight. 1 may be an oxygen atom.

[0027] The olefin polymerization catalyst of the present invention may further contain the following component (B). Component (B): Organoaluminum compound.

[0028] Another embodiment of the present invention provides a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention. In the method for producing an olefin polymer of the present invention, the olefin may be propylene. [Effects of the Invention]

[0029] According to the present invention, there can be provided a novel metal complex, a catalyst component, which is used for producing olefin, particularly propylene polymers and copolymers, and which gives polymers with high activity and higher molecular weight, as well as a method for producing olefin, particularly propylene polymers and copolymers, using the same. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention provides a metal complex which is a reaction product of a compound represented by general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, Group 10 or Group 11 of the periodic table, such as Ni (nickel), Pd (palladium), Co (cobalt), Cu (copper) or Rh (rhodium); a metal complex represented by general formula [III]; an olefin polymerization catalyst component containing such a metal complex; a catalyst using such a metal complex as a catalyst component; and a method for producing an olefin polymer or copolymer in the presence of such a 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 particular need to distinguish between the two, they are collectively referred to simply as "polymerization." Furthermore, 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" to indicate a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit.

[0031] 1. Metal complexes The metal complex of the present invention is a reaction product between a compound represented by the following general formula [I] or [II] and a transition metal compound containing a transition metal belonging to Group 9, 10 or 11 of the periodic table.

[0032] [ka] [R in formula [I] and [II] 1 ~R 6 , E 1 , and X 1 is as follows: R 1 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms. R 2 , R 3 and R 4each independently represents an atom or group selected from the group consisting of the following (i) to (iv): (i) Hydrogen atom (ii) halogen atoms (iii) A linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of heteroatoms and groups containing heteroatoms. (iv) OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 9 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 8 )2M', or an epoxy-containing group, where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. 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 an oxygen atom, a nitrogen atom, and a sulfur atom, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. R 5 or R 6 each independently represents a fused polycyclic hydrocarbon group which may have a substituent. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom, a sulfur atom, or SO3. In addition, in the general formula [I], Z represents a hydrogen atom or a leaving group; m represents the valence of Z.]

[0033] The reaction product of the compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10 or 11 of the periodic table, which is the metal complex of the present invention, can be obtained, for example, by contacting the compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10 or 11 of the periodic table. In the present invention, "contact" means contacting E in the general formula [I] or [II]. 1 can form a coordinate bond with the transition metal, and / or X in these general formulas 1 means that the compound represented by the general formula [I] or [II] and the transition metal compound are present in sufficient proximity to each other so that a single bond can be formed between the compound represented by the general formula [I] or [II] and the transition metal compound. Contacting the compound represented by the general formula [I] or [II] and the transition metal compound means mixing these compounds so that they are present in sufficient proximity to each other and at least one of the two types of bonds can be formed. The conditions for mixing the compound represented by the general formula [I] or [II] with the transition metal compound are not particularly limited. These compounds may be mixed directly or in a solvent. In particular, it is preferable to use a solvent in order to achieve uniform mixing. In the resulting metal complex, the compound represented by the general formula [I] or [II] serves as a ligand, and therefore the reaction between the compound represented by the general formula [I] or [II] and the transition metal compound is usually a ligand exchange reaction. When the resulting metal complex is more thermodynamically stable than the transition metal compound, the ligand exchange reaction proceeds by mixing the compound represented by the general formula [I] or [II] and the transition metal compound at room temperature (15 to 30°C). On the other hand, when the resulting metal complex is more thermodynamically unstable than the transition metal compound, it is preferable to appropriately heat the mixture to sufficiently promote the ligand exchange reaction.

[0034] The metal complex obtained by contacting the compound represented by general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10 or 11 of the periodic table is presumed to have a structure represented by general formula [III] described below. However, since the compounds represented by general formula [I] or [II] are bidentate ligands, when the compounds are brought into contact with a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table, a metal complex having a structure other than that represented by general formula [III] may be produced. For example, X in general formula [I] or [II] 1 When only E forms a bond with a transition metal, 1It is also possible that only one molecule of the compound represented by general formula [I] or [II] forms a bond with the transition metal. Furthermore, while the metal complex represented by general formula [III] is a 1:1 reaction product between a compound represented by general formula [I] or [II] and a transition metal compound, it is also possible that a reaction product with a different composition ratio may be obtained depending on the type of transition metal. For example, it is also possible that two or more molecules of the compound represented by general formula [I] or [II] form a complex with one transition metal, or that one molecule of the compound represented by general formula [I] or [II] 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 [III] can be used for producing olefin (co)polymers in the same manner as the metal complexes represented by general formula [III].

[0035] By using the metal complex of the present invention, olefin (co)polymers having higher molecular weights, in particular propylene (co)polymers having higher molecular weights, can be obtained with high activity. E that can react with central metal M 1 a bulky X having two bulky fused polycyclic hydrocarbon groups thereon and capable of reacting with a transition metal; 1 Ortho position (R 1 ) has a specific hydrocarbon group, which appropriately controls the steric crowding around the central metal M, thereby suppressing β-hydrogen elimination and improving the molecular weight of the resulting polymer chain. It is presumed that due to these synergistic effects, the use of the metal complex of the present invention makes it possible to obtain an olefin (co)polymer with higher activity and higher molecular weight.

[0036] Hereinafter, R in the general formulas [I] and [II] 1 ~R 6 , E 1 , X 1 and Z and m in general formula [I] will be explained. R 1represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms. The upper limit of the number of carbon atoms in each of the linear alkyl group, branched acyclic alkyl group, alkenyl group, cycloalkyl group which may have a side chain, aryl group, arylalkyl group, and alkylaryl group is preferably 25, more preferably 20, and even more preferably 15.

[0037] R 1 Among these examples, examples of the linear alkyl group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 10 carbon atoms such as 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. R 1 Among these examples, examples of the branched acyclic alkyl group having 3 to 30 carbon atoms include branched acyclic alkyl groups having 3 to 10 carbon atoms such as an isopropyl group, an isobutyl group, a tert-butyl group (t-butyl group), a sec-butyl group, an isopentyl group (3-methylbutyl group), a t-pentyl group (1,1-dimethylpropyl group), a sec-pentyl group (1-methylbutyl group), a 2-methylbutyl group, a neopentyl group (2,2-dimethylpropyl group), a 1,2-dimethylpropyl group, and an isohexyl group (4-methylpentyl group), and may be a branched acyclic alkyl group having 3 to 8 carbon atoms. R 1 Among these examples, 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 be an alkenyl group having 3 to 8 carbon atoms such as an allyl group, a butenyl group, a pentenyl group, a hexenyl group, or a styryl group, or may be an alkenyl group having 4 to 8 carbon atoms such as a butenyl group, a pentenyl group, a hexenyl group, or a styryl group.

[0038] R 1Among these examples, examples of the cycloalkyl group which may have a side chain having 3 to 30 carbon atoms include a cycloalkyl group which may have a side chain having 3 to 10 carbon atoms, such as 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 cyclooctyl group, or a decahydronaphthyl group (bicyclo[4,4,0]decyl group), and may be a cycloalkyl group which may have a side chain having 3 to 6 carbon atoms. R 1 Among these examples, examples of the aryl group having 6 to 30 carbon atoms include aryl groups having 6 to 18 carbon atoms, such as 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, and may be an aryl group having 6 to 12 carbon atoms. R 1 Among these examples, examples of the arylalkyl group having 7 to 30 carbon atoms include an arylalkyl group having 7 to 15 carbon atoms, such as a benzyl group, a phenethyl group (2-phenylethyl group), a 9-fluorenyl group, a naphthylmethyl group, and a 1-tetralinyl group, and may be an arylalkyl group having 7 to 10 carbon atoms.

[0039] R 1Among the examples, 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 tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl groups.

[0040] R 1 In terms of providing a polymer with high activity and a high molecular weight, the group is preferably a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, more preferably an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms, and even more preferably an alkylaryl group having 7 to 30 carbon atoms.

[0041] R 1 Among these, from the viewpoint of providing a polymer with high activity and a high molecular weight, preferred are 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 12 carbon atoms, more preferred are alkylaryl groups 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 12 carbon atoms, and even more preferred are substituents represented by the following general formula (1):

[0042] [ka] (In the general formula (1), R a each independently represents a linear or branched acyclic alkyl group having two or more carbon atoms; R b each independently represents a hydrogen atom or a linear or branched acyclic alkyl group, and * represents a bond.

[0043] In general formula (1), R a The linear or branched acyclic alkyl group having 2 or more carbon atoms in the formula (I) may be a linear or branched acyclic alkyl group having 2 or more and 10 or less carbon atoms, and examples thereof include linear alkyl groups having 2 to 10 carbon atoms, such as an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group, and branched acyclic alkyl groups having 3 to 10 carbon atoms, such as an isopropyl group, isobutyl group, tert-butyl group (t-butyl group), sec-butyl group, isopentyl group (3-methylbutyl group), t-pentyl group (1,1-dimethylpropyl group), sec-pentyl group (1-methylbutyl group), 2-methylbutyl group, neopentyl group (2,2-dimethylpropyl group), 1,2-dimethylpropyl group, and isohexyl group (4-methylpentyl group). In general formula (1), R b The linear or branched acyclic alkyl group in R may be a linear or branched acyclic alkyl group having 1 to 10 carbon atoms, a In addition to the alkyl groups mentioned above, a methyl group may also be used.

[0044] R 1Examples of the substituent represented by general formula (1) in the above formula (1) include a 2,6-diethylphenyl group, a 2,6-di-n-propylphenyl group, a 2,6-di-n-butylphenyl group, a 2,6-di-n-pentylphenyl group, a 2,6-di-n-hexylphenyl group, a 2,6-diisopropylphenyl group, a 2,6-diisobutylphenyl group, a 2,6-di-t-butylphenyl group, a 2,6-di-sec-butylphenyl group, a 2,6-diisopentylphenyl group, a 2,6-di-t-pentylphenyl group, a 2,6-di-sec-pentylphenyl group, a 2,4,6-triethylphenyl group, a 2,4,6-tri-n-propylphenyl group, a 2,4,6-tri-isopropylphenyl group, and a 2,4,6-tri-n-butylphenyl group. Among these, more preferred are 2,6-diisopropylphenyl and 2,6-di-t-butylphenyl groups, and R 1 More preferably, is a 2,6-diisopropylphenyl group.

[0045] 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 atoms (iii) A linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of heteroatoms and groups containing heteroatoms. (iv) OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR9 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 8 )2M', or an epoxy-containing group, where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. R 2 , R 3 and R 4 Adjacent 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 an oxygen atom, a nitrogen atom, and a sulfur atom, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring.

[0046] (ii) Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Among these, fluorine atoms are preferred.

[0047] Examples of heteroatoms used in (iii) include oxygen, nitrogen, phosphorus, sulfur, selenium, silicon, halogen, and boron atoms. Among these heteroatoms, fluorine and chlorine atoms are preferred. Specific examples of the "group containing a hetero atom" used in (iii) include the same groups as those of the hetero atom-containing substituent (iv) described below. Examples of the "group containing a hetero atom" include an alkoxy group (OR 9 ), ester group (CO2R 9 ) etc. In addition, R 9 is as described below. In the above (iii), R 2 ~R 4 The total number of carbon atoms in the substituents corresponding to the following formula is preferably 1 to 30, more preferably 2 to 25, and even more preferably 4 to 20. In light of the above, (iii) "a specific group which may have a 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, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms, (iii-B) each of the groups in (iii-A) above with one or more heteroatoms substituted thereto, (iii-C) each of the groups in (iii-A) above with one or more "groups containing a heteroatom" substituted thereto, and (iii-D) each of the groups in (iii-A) above with one or more heteroatoms and one or more "groups containing a heteroatom" substituted thereto. Examples of (iii-C) include an alkyl group substituted with an alkoxy group and an aryl group substituted with an ester group.

[0048] (iv) The heteroatom-containing substituent specifically includes OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 9 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 )x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 8 )2M', and an epoxy-containing group, where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 represents a hydrocarbon group having 1 to 20 carbon atoms. In the present invention, hydrocarbon groups include saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons, and examples of hydrocarbon groups having 1 to 20 carbon atoms include the above-mentioned linear alkyl groups, branched acyclic alkyl groups, alkenyl groups, cycloalkyl groups which may have a side chain, aryl groups, arylalkyl groups, and alkylaryl groups which have 1 to 20 carbon atoms. M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2.

[0049] R 2 ,R 3 and R 4 are 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 isopropyl group, a butyl group, a phenyl group, a trifluoromethyl group, a pentafluorophenyl group, a naphthyl group, or an anthracenyl group; or (iv) a methoxy group, an ethoxy group, a phenoxy group, a nitrile group, a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, a trimethylsilyloxy group, a trimethoxysiloxy group, a cyclohexylamino group, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, or the like. Among these, particularly preferred are (i) a hydrogen atom; (iii) a methyl group, an isobutyl group, a tert-butyl group (t-butyl group), a sec-butyl group, and a pentafluorophenyl group; and (iv) a methoxy group, a trimethylsilyl group, a trimethylsilyloxy group, and a cyclohexylamino group. 3is preferably a hydrogen atom, a methyl group, or a t-butyl group, and R 3 is more preferably a hydrogen atom or a t-butyl group.

[0050] In addition, R 2 ,R 3 and R 4 Adjacent 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 which case the ring has 5 to 8 members and may or may not have a substituent on the ring. Also, R 2 The groups contained within R are linked to each other. 2 A ring may be formed on the R 3 , or R 4 The same applies when any one of the groups contains multiple groups.

[0051] R 5 and R 6 each independently represents a fused polycyclic hydrocarbon group which may have a substituent. Examples of the fused polycyclic hydrocarbon group include fused polycyclic hydrocarbon groups formed by condensing two rings, such as a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, and a heptalenyl group; and fused polycyclic hydrocarbon groups formed by condensing three rings, such as a biphenylenyl group, an as-indacenyl group, an s-indacenyl group, an acenaphthylenyl group, a fluorenyl group, a phenalenyl group, a phenanthryl group, an anthracenyl group, and a 9,10-dihydroanthracenyl group. fused polycyclic hydrocarbon groups formed by condensing four rings, such as a fluoranthenyl group, an acephenanthrilenyl group, an aceanthrlenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, or a pleiadenyl group; and fused polycyclic hydrocarbon groups formed by condensing five rings, such as a picenyl group, a perylenyl group, a pentaphenyl group, a pentacenyl group, or a tetraphenylenyl group. As the fused polycyclic hydrocarbon group, from the viewpoint of providing a polymer with high activity and a high molecular weight, a fused polycyclic hydrocarbon group formed by condensing three or more rings is preferred, a fused polycyclic hydrocarbon group formed by condensing three rings is more preferred, at least one of a fluorenyl group, an as-indacenyl group, an s-indacenyl group, a phenanthryl group, an anthracenyl group, and a 9,10-dihydroanthracenyl group is even more preferred, and a fluorenyl group or a 9,10-dihydroanthracenyl group is even more preferred.

[0052] Each of the fused polycyclic hydrocarbon groups may have a substituent. Examples of the substituent may be an atom or group selected from the group consisting of (ii) to (iv) above, and may be a substituent selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 20 carbon atoms substituted with an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. The hydrocarbon group here may be the same as described above. The substituent of the condensed polycyclic hydrocarbon group is preferably a fluorine atom, a chlorine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, a benzyl group, a phenyl group; a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group; a methoxy group, an ethoxy group, a 1-propoxy group, an isopropoxy group, a 1-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group, a methoxymethyl group, a 2-methylpropyl ... Examples of such groups include ethoxyethyl, isopropoxymethyl, 2-isopropoxyethyl, 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl groups; phenoxymethyl, 2-phenoxyethyl, 2-phenoxyphenyl, 3-phenoxyphenyl, and 4-phenoxyphenyl groups; methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, isobutoxy, sec-butoxy, t-butoxy, and pentyloxy groups; and phenoxy, 1-naphthoxy, and 2-naphthoxy groups.

[0053] R 5 and R 6 are each independently preferably an optionally substituted fluorenyl group or an optionally substituted 9,10-dihydroanthracenyl group, from the viewpoint of providing a polymer with high activity and a high molecular weight, and among these, preferably include a substituent represented by the following general formula (2) or (3):

[0054] [ka] (In the general formula (2), R c , R d , R e , R f , R g , R h , R i , and R jeach independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 20 carbon atoms substituted with an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. * represents a bond.

[0055] R c , R d , R e , R f , R g , R h , R i , and R j may each independently be a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. R c , R d , R e , R f , R g , R h , R i , and R j are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear alkyl group or a branched acyclic alkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a linear alkyl group or a branched acyclic alkyl group having 1 to 4 carbon atoms. In general formula (2), in view of the influence of steric hindrance, the number of substituents other than hydrogen atoms is preferably 3 or less, and more preferably 2 or less. Also, R c , R d , R e , R f , R g , R h , R i , and R j Are all hydrogen atoms? c , R e , R f , Rg , R h , and R j are hydrogen atoms, and R d and R i are each independently a hydrocarbon group having 1 to 10 carbon atoms; and R c , R d , R f , R g , R i , and R j are hydrogen atoms, and R e and R h are each independently a hydrocarbon group having 1 to 10 carbon atoms; R c , R d , R e , R h , R i , and R j are hydrogen atoms, and R f and R g are each independently a hydrocarbon group having 1 to 10 carbon atoms, from the viewpoint of the influence of steric hindrance.

[0056] Specific examples of the general formula (2) include a 9-fluorenyl group, a 1-methyl-9-fluorenyl group, a 2-methyl-9-fluorenyl group, a 3-methyl-9-fluorenyl group, a 4-methyl-9-fluorenyl group, a 1-ethyl-9-fluorenyl group, a 2-ethyl-9-fluorenyl group, a 3-ethyl-9-fluorenyl group, a 4-ethyl-9-fluorenyl group, a 1-n-propyl-9-fluorenyl group, a 2-n-propyl-9-fluorenyl group, a 3-n-propyl-9-fluorenyl group, a 4-n-propyl-9-fluorenyl group, a 1-ethyl-9-fluorenyl group, a 2-ethyl ... fluorenyl group, 1-isopropyl-9-fluorenyl group, 2-isopropyl-9-fluorenyl group, 3-isopropyl-9-fluorenyl group, 4-isopropyl-9-fluorenyl group, 1-n-butyl-9-fluorenyl group, 2-n-butyl-9-fluorenyl group, 3-n-butyl-9-fluorenyl group, 4-n-butyl-9-fluorenyl group, 1-isobutyl-9-fluorenyl group, 2-isobutyl-9-fluorenyl group, 3-isobutyl-9-fluorenyl group, 4-isobutyl-9-fluorenyl group , 1-sec-butyl-9-fluorenyl group, 2-sec-butyl-9-fluorenyl group, 3-sec-butyl-9-fluorenyl group, 4-sec-butyl-9-fluorenyl group, 1-t-butyl-9-fluorenyl group, 2-t-butyl-9-fluorenyl group, 3-t-butyl-9-fluorenyl group, 4-t-butyl-9-fluorenyl group, 1-methoxy-9-fluorenyl group, 2-methoxy-9-fluorenyl group, 3-methoxy-9-fluorenyl group, 4-methoxy-9-fluorenyl group, 1-ethoxy-9-fluorenyl group, 2-ethoxy-9-fluorenyl group, 3-ethoxy-9-fluorenyl group, 4-ethoxy-9-fluorenyl group, ethoxy-9-fluorenyl group, 2-ethoxy-9-fluorenyl group, 3-ethoxy-9-fluorenyl group, 4-ethoxy-9-fluorenyl group, 1-phenoxy-9-fluorenyl group, 2-phenoxy-9-fluorenyl group, 3-phenoxy-9-fluorenyl group, 4-phenoxy-9-fluorenyl group, 1-trifluoromethyl-9-fluorenyl group, 2-trifluoromethyl-9-fluorenyl group, 3-trifluoromethyl-9-fluorenyl group, 4-trifluoromethyl-9-fluorenyl group,

[0057] 1,2-dimethyl-9-fluorenyl group, 1,3-dimethyl-9-fluorenyl group, 1,4-dimethyl-9-fluorenyl group, 1,5-dimethyl-9-fluorenyl group, 1,6-dimethyl-9-fluorenyl group, 1,7-dimethyl-9-fluorenyl group, 1,8-dimethyl-9-fluorenyl group, 2,3-dimethyl-9-fluorenyl group, 2,4-dimethyl-9-fluorenyl group, 2,5-dimethyl-9-fluorenyl group, 2,6-dimethyl-9-fluorenyl group, 2,7-dimethyl-9-fluorenyl group, 3,4-dimethyl-9-fluorenyl group, 3 ,5-dimethyl-9-fluorenyl group, 3,6-dimethyl-9-fluorenyl group, 4,5-dimethyl-9-fluorenyl group, 1,2-diethyl-9-fluorenyl group, 1,3-diethyl-9-fluorenyl group, 1,4-diethyl-9-fluorenyl group, 1,5-diethyl-9-fluorenyl group, 1,6-diethyl-9-fluorenyl group, 1,7-diethyl-9-fluorenyl group, 1,8-diethyl-9-fluorenyl group, 2,3-diethyl-9-fluorenyl group, 2,4-diethyl-9-fluorenyl group, 2,5-diethyl-9-fluorenyl group, 2,6 -diethyl-9-fluorenyl group, 2,7-diethyl-9-fluorenyl group, 3,4-diethyl-9-fluorenyl group, 3,5-diethyl-9-fluorenyl group, 3,6-diethyl-9-fluorenyl group, 4,5-diethyl-9-fluorenyl group, 1,2-di(n-propyl)-9-fluorenyl group, 1,3-di(n-propyl)-9-fluorenyl group, 1,4-di(n-propyl)-9-fluorenyl group, 1,5-di(n-propyl)-9-fluorenyl group, 1,6-di(n-propyl)-9-fluorenyl group, 1,7-di(n-propyl)-9-fluorenyl group fluorenyl group, 1,8-di(n-propyl)-9-fluorenyl group, 2,3-di(n-propyl)-9-fluorenyl group, 2,4-di(n-propyl)-9-fluorenyl group, 2,5-di(n-propyl)-9-fluorenyl group, 2,6-di(n-propyl)-9-fluorenyl group, 2,7-di(n-propyl)-9-fluorenyl group, 3,4-di(n-propyl)-9-fluorenyl group, 3,5-di(n-propyl)-9-fluorenyl group, 3,6-di(n-propyl)-9-fluorenyl group, 4,5-di(n-propyl)-9-fluorenyl group, 1,2-diisopropyl-9-fluorenyl group, 1,3-diisopropyl-9-fluorenyl group, 1,4-diisopropyl-9-fluorenyl group, 1,5-diisopropyl-9-fluorenyl group, 1,6-diisopropyl-9-fluorenyl group, 1,7-diisopropyl-9-fluorenyl group, 1,8-diisopropyl-9-fluorenyl group, 2,3-diisopropyl-9-fluorenyl group, 2,4-diisopropyl-9-fluorenyl group, 2,5-diisopropyl-9-fluorenyl group, 2,6-diisopropyl-9-fluorenyl group, 2,7-diisopropyl-9-fluorenyl group, 3,4-diisopropyl-9-fluorenyl group, 3,5-diisopropyl-9-fluorenyl group, 3,6-diisopropyl-9-fluorenyl group, 4,5-diisopropyl-9-fluorenyl group,

[0058] 1,2-di-t-butyl-9-fluorenyl group, 1,3-di-t-butyl-9-fluorenyl group, 1,4-di-t-butyl-9-fluorenyl group, 1,5-di-t-butyl-9-fluorenyl group, 1,6-di-t-butyl-9-fluorenyl group, 1,7-di-t-butyl-9-fluorenyl group, 1,8-di-t-butyl-9-fluorenyl group, 2,3-di-t-butyl-9-fluorenyl group fluorenyl group, 2,4-di-t-butyl-9-fluorenyl group, 2,5-di-t-butyl-9-fluorenyl group, 2,6-di-t-butyl-9-fluorenyl group, 2,7-di-t-butyl-9-fluorenyl group, 3,4-di-t-butyl-9-fluorenyl group, 3,5-di-t-butyl-9-fluorenyl group, 3,6-di-t-butyl-9-fluorenyl group, 4,5-di(t-butyl) Examples of the fluorenyl group include a 1,2-dimethoxy-9-fluorenyl group, a 1,3-dimethoxy-9-fluorenyl group, a 1,4-dimethoxy-9-fluorenyl group, a 1,5-dimethoxy-9-fluorenyl group, a 1,6-dimethoxy-9-fluorenyl group, a 1,7-dimethoxy-9-fluorenyl group, a 1,8-dimethoxy-9-fluorenyl group, a 2,3-dimethoxy-9-fluorenyl group, a 2,4-dimethoxy-9-fluorenyl group, a 2,5-dimethoxy-9-fluorenyl group, a 2,6-dimethoxy-9-fluorenyl group, a 2,7-dimethoxy-9-fluorenyl group, a 3,4-dimethoxy-9-fluorenyl group, a 3,5-dimethoxy-9-fluorenyl group, a 3,6-dimethoxy-9-fluorenyl group, and a 4,5-dimethoxy-9-fluorenyl group.

[0059] Of these, preferred are 9-fluorenyl group, 2,7-dimethyl-9-fluorenyl group, 2,7-di-t-butyl-9-fluorenyl group, 3,6-dimethyl-9-fluorenyl group, 3,6-di-t-butyl-9-fluorenyl group, 4,5-dimethyl-9-fluorenyl group, and 4,5-di-t-butyl-9-fluorenyl group, and particularly preferred are 9-fluorenyl group and 3,6-di-t-butyl-9-fluorenyl group.

[0060] [ka] (In the general formula (3), R k , R l , R m , R n , R o , R p , R q , R r , R s , and R t each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 20 carbon atoms substituted with an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. * represents a bond.

[0061] R k , R l , R m , R n , R o , R p , R q , R r , R s , and R t may each independently be a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, an alkoxy group having 1 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. R k , R l , R m , R n , R o , R p , R q , R r , R s , and R t are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear alkyl group or a branched acyclic alkyl group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a linear alkyl group or a branched acyclic alkyl group having 1 to 4 carbon atoms. In general formula (3), in view of the influence of steric hindrance, the number of substituents other than hydrogen atoms is preferably 3 or less, and more preferably 2 or less.

[0062] Also, R k , R l , R m , R n , R o , R p , R q , R r , R s , and R t Are all hydrogen atoms? k , R l , R m , R n , R q , R r , R s , R t and R o are hydrogen atoms, and R p is a hydrocarbon group having 1 to 10 carbon atoms; R k , R l , R m , R n , R q , R r , R s , and R t are hydrogen atoms, and R o and R p are each independently a hydrocarbon group having 1 to 10 carbon atoms; R k , R l , R m , R o , R p , R r , R s , and R t are hydrogen atoms, and R n and R q are each independently a hydrocarbon group having 1 to 10 carbon atoms; R k , R l , R n , R o , R p , R q , R s , and R t are hydrogen atoms, and R m and R rare each independently a hydrocarbon group having 1 to 10 carbon atoms; R k , R m , R n , R o , R p , R q , R r , and R t are hydrogen atoms, and R l and R s are each independently a hydrocarbon group having 1 to 10 carbon atoms, from the viewpoint of the influence of steric hindrance.

[0063] Specific examples of the general formula (3) include 9,10-dihydro-9-anthracenyl group, 1-methyl-9,10-dihydro-9-anthracenyl group, 2-methyl-9,10-dihydro-9-anthracenyl group, 3-methyl-9,10-dihydro-9-anthracenyl group, 4-methyl-9,10-dihydro-9-anthracenyl group, 1-ethyl-9,10-dihydro-9-anthracenyl group, 2-ethyl-9,10-dihydro-9-anthracenyl group, 3-ethyl-9,10-dihydro-9-anthracenyl group, 4-ethyl-9,10-dihydro- 9-anthracenyl group, 1-n-propyl-9,10-dihydro-9-anthracenyl group, 2-n-propyl-9,10-dihydro-9-anthracenyl group, 3-n-propyl-9,10-dihydro-9-anthracenyl group, 4-n-propyl-9,10-dihydro-9-anthracenyl group, 1-isopropyl-9,10-dihydro-9-anthracenyl group, 2-isopropyl-9,10-dihydro-9-anthracenyl group, 3-isopropyl-9,10-dihydro-9-anthracenyl group, 4-isopropyl-9,10-dihydro-9 -anthracenyl group, 1-n-butyl-9,10-dihydro-9-anthracenyl group, 2-n-butyl-9,10-dihydro-9-anthracenyl group, 3-n-butyl-9,10-dihydro-9-anthracenyl group, 4-n-butyl-9,10-dihydro-9-anthracenyl group, 1-isobutyl-9,10-dihydro-9-anthracenyl group, 2-isobutyl-9,10-dihydro-9-anthracenyl group, 3-isobutyl-9,10-dihydro-9-anthracenyl group, 4-isobutyl-9,10-dihydro-9-anthracenyl group , 1-sec-butyl-9,10-dihydro-9-anthracenyl group, 2-sec-butyl-9,10-dihydro-9-anthracenyl group, 3-sec-butyl-9,10-dihydro-9-anthracenyl group, 4-sec-butyl-9,10-dihydro-9-anthracenyl group, 1-t-butyl-9,10-dihydro-9-anthracenyl group, 2-t-butyl-9,10-dihydro-9-anthracenyl group, 3-t-butyl-9,10-dihydro-9-anthracenyl group, 4-t-butyl-9,10-dihydro-9-anthracenyl group,

[0064] 1-Methoxy-9,10-dihydro-9-anthracenyl group, 2-Methoxy-9,10-dihydro-9-anthracenyl group, 3-Methoxy-9,10-dihydro-9-anthracenyl group, 4-Methoxy-9,10-dihydro-9-anthracenyl group, 1-Ethoxy-9,10-dihydro-9-anthracenyl group, 2-Ethoxy-9,10-dihydro-9-anthracenyl group, 3-Ethoxy-9,10-dihydro-9-anthracenyl group, 4-Ethoxy-9,10-dihydro-9-anthracenyl group, 1-Phenoxy-9,10 -dihydro-9-anthracenyl group, 2-phenoxy-9,10-dihydro-9-anthracenyl group, 3-phenoxy-9,10-dihydro-9-anthracenyl group, 4-phenoxy-9,10-dihydro-9-anthracenyl group, 1-trifluoromethyl-9,10-dihydro-9-anthracenyl group, 2-trifluoromethyl-9,10-dihydro-9-anthracenyl group, 3-trifluoromethyl-9,10-dihydro-9-anthracenyl group, 4-trifluoromethyl-9,10-dihydro-9-anthracenyl group,

[0065] 1,2-dimethyl-9,10-dihydro-9-anthracenyl group, 1,3-dimethyl-9,10-dihydro-9-anthracenyl group, 1,4-dimethyl-9,10-dihydro-9-anthracenyl group, 1,5-dimethyl-9,10-dihydro-9-anthracenyl group, 1,6-dimethyl-9,10-dihydro-9-anthracenyl group, 1,7-dimethyl-9,10-dihydro-9-anthracenyl group, 1,8-dimethyl-9,10-dihydro-9-anthracenyl group, 2,3-dimethyl-9,10-dihydro-9-anthracenyl group, 2,4-dimethyl-9,10-dihydro-9-anthracenyl group, 2,5-dimethyl-9,10-dihydro-9-anthracenyl group, 2,6-dimethyl-9,10-dihydro-9-anthracenyl group, 2,7-dimethyl-9,10-dihydro-9-anthracenyl group, 3,4-dimethyl-9,10-dihydro-9-anthracenyl group, 3,5-dimethyl-9,10-dihydro-9-anthracenyl group, 3,6-dimethyl-9,10-dihydro-9-anthracenyl group, 4,5-dimethyl-9,10-dihydro-9-anthracenyl group, 1,2-diethyl-9,10-dihydro-9-anthracenyl group, 1,3-diethyl-9,10-dihydro-9-anthracenyl group, 1,4-diethyl-9,10-dihydro-9-anthracenyl group, 1,5-diethyl-9,10-dihydro-9-anthracenyl group, 1,6-diethyl-9,10-dihydro-9-anthracenyl group, 1,7-diethyl-9,10-dihydro-9-anthracenyl group, 1,8-diethyl-9,10-dihydro-9-anthracenyl group, 2,3-diethyl-9,10-dihydro-9-anthracenyl group, 2,4-diethyl-9,10-dihydro-9-anthracenyl group, 2,5-diethyl-9,10-dihydro-9-anthracenyl group, 2,6-diethyl-9,10-dihydro-9-anthracenyl group, 2,7-diethyl-9,10-dihydro-9-anthracenyl group, 3,4-diethyl-9,10-dihydro-9-anthracenyl group, 3,5-diethyl-9,10-dihydro-9-anthracenyl group, 3,6-diethyl-9,10-dihydro-9-anthracenyl group, 4,5-diethyl-9,10-dihydro-9-anthracenyl group,

[0066] 1,2-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,3-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,4-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,5-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,6-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,7-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,8-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 2, 3-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 2,4-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 2,5-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 2,6-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 2,7-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 3,4-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 3,5-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 3,6-di (n-propyl)-9,10-dihydro-9-anthracenyl group, 4,5-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 1,2-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,3-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,4-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,5-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,6-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,7-diisopropyl-9,10-di dihydro-9-anthracenyl group, 1,8-diisopropyl-9,10-dihydro-9-anthracenyl group, 2,3-diisopropyl-9,10-dihydro-9-anthracenyl group, 2,4-diisopropyl-9,10-dihydro-9-anthracenyl group, 2,5-diisopropyl-9,10-dihydro-9-anthracenyl group, 2,6-diisopropyl-9,10-dihydro-9-anthracenyl group, 2,7-diisopropyl-9,10-dihydro-9-anthracenyl group, 3,4-diisopropyl-9,10-dihydro-9-anthracenyl group, 3,5-diisopropyl-9,10-dihydro-9-anthracenyl group, 3,6-diisopropyl-9,10-dihydro-9-anthracenyl group, 4,5-diisopropyl-9,10-dihydro-9-anthracenyl group, 1,2-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,3-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,4-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,5-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,6-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,7-di-t-butyl-9,10-dihydro-9-anthracenyl group, 1,8-di-t-butyl-9,10-di 2,3-di-t-butyl-9,10-dihydro-9-anthracenyl group, 2,4-di-t-butyl-9,10-dihydro-9-anthracenyl group, 2,5-di-t-butyl-9,10-dihydro-9-anthracenyl group, 2,6-di-t-butyl-9,10-dihydro-9-anthracenyl group, 2,7-di-t-butyl 3,4-di-t-butyl-9,10-dihydro-9-anthracenyl group, 3,5-di-t-butyl-9,10-dihydro-9-anthracenyl group, 3,6-di-t-butyl-9,10-dihydro-9-anthracenyl group, 4,5-di(t-butyl)-9,10-dihydro-9-anthracenyl group,

[0067] 1,2-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,3-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,4-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,5-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,6-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,7-dimethoxy-9,10-dihydro-9-anthracenyl group, 1,8-dimethoxy-9,10-dihydro-9-anthracenyl group, 2,3-dimethoxy-9,10-dihydro-9-anthracenyl group, 2,4-dimethoxy-9,10-dihydro-9-anthracenyl group, 2,5-dimethoxy-9,10-dihydro-9-anthracenyl group, 2,6-dimethoxy-9,10-dihydro-9-anthracenyl group, 2,7-dimethoxy-9,10-dihydro-9-anthracenyl group, 3,4-dimethoxy-9,10-dihydro-9-anthracenyl group, 3,5-dimethoxy-9,10-dihydro-9-anthracenyl group, 3,6-dimethoxy-9,10-dihydro-9-anthracenyl group, 4,5-dimethoxy-9,10-dihydro-9-anthracenyl group,

[0068] 10-methyl-9,10-dihydro-9-anthracenyl group, 10-ethyl-9,10-dihydro-9-anthracenyl group, 10-n-propyl-9,10-dihydro-9-anthracenyl group, 10-isopropyl-9,10-dihydro-9-anthracenyl group, 10-n-butyl-9,10-dihydro-9-anthracenyl group, 10-isobutyl-9,10-dihydro-9-anthracenyl group, 10-sec-butyl 10-t-butyl-9,10-dihydro-9-anthracenyl group, 10-methoxy-9,10-dihydro-9-anthracenyl group, 10-ethoxy-9,10-dihydro-9-anthracenyl group, 10-phenoxy-9,10-dihydro-9-anthracenyl group, 10-trifluoromethyl-9,10-dihydro-9-anthracenyl group, 10-dimethyl-9,10- Dihydro-9-anthracenyl group, 10-diethyl-9,10-dihydro-9-anthracenyl group, 10-di(n-propyl)-9,10-dihydro-9-anthracenyl group, 10-diisopropyl-9,10-dihydro-9-anthracenyl group, 10-di(n-butyl)-9,10-dihydro-9-anthracenyl group, 10-diisobutyl-9,10-dihydro-9-anthracenyl group, 10-di(sec-butyl) 10-di(t-butyl)-9,10-dihydro-9-anthracenyl group, 10-dimethoxy-9,10-dihydro-9-anthracenyl group, 10-diethoxy-9,10-dihydro-9-anthracenyl group, 10-diphenoxy-9,10-dihydro-9-anthracenyl group, and 10-ditrifluoromethyl-9,10-dihydro-9-anthracenyl group.

[0069] Of these, preferred are 9,10-dihydro-9-anthracenyl group, 2,7-dimethyl-9,10-dihydro-9-anthracenyl group, 2,7-di-t-butyl-9,10-dihydro-9-anthracenyl group, 3,6-dimethyl-9,10-dihydro-9-anthracenyl group, 3,6-di-t-butyl-9,10-dihydro-9-anthracenyl group, 4,5-dimethyl-9,10-dihydro-9-anthracenyl group, 4,5-di-t-butyl-9,10-dihydro-9-anthracenyl group, 10-methyl-9,10-dihydro-9-anthracenyl group, and 10-dimethyl-9,10-dihydro-9-anthracenyl group, and particularly preferred is 9,10-dihydro-9-anthracenyl group.

[0070] 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, a sulfur atom, or SO3. 1 is preferably an oxygen atom in terms of acidity for deprotonation. Z represents a hydrogen atom or a leaving group. Specifically, Z represents a hydrogen atom, a halogen atom, or R 9 SO2 group (where R 9 The halogen atom may be a bromine atom or an iodine atom, and R 9 Specific examples of the SO2 group include a tosyl group (p-toluenesulfonyl group) and a mesyl group (methanesulfonyl group). m represents the valence of Z.

[0071] The general formula [II] is expressed in the form of an anion, but any counter cation can be used as long as it does not inhibit the reaction with the transition metal compound in the present invention. Specific examples of the counter cation include ammonium, quaternary ammonium, phosphonium, and metal ions of Groups 1 to 14 of the periodic table. Among these, NH4+ , R 9 4N + (where R 9 is as described above, and the four R 9 may be the same or different. The same applies below.) 9 4P + , Li + , Na + , K. + , Mg 2+ , Ca 2+ , Al 3+ and more preferably, R 9 4N + , Li + , Na + , K. + is.

[0072] Specific combinations of substituents and the like in the general formulas [I] and [II] of the present invention are shown in the following Tables 1 and 2. Z and m relate only to the general formula [I]. However, specific examples are not limited to the following examples.

[0073] [Table 1]

[0074] [Table 2]

[0075] The compounds represented by the general formulas [I] and [II] can be synthesized based on known synthesis methods.

[0076] The transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table used in the present invention is one that can react with the compound represented by general formula [I] or [II] to form a polymerizable complex. These are sometimes called precursors. As the transition metal compound containing a transition metal of Group 9, 10 or 11, a transition metal compound represented by the following general formula [IV] can be used. General formula [IV]:MR 7’ p L 1 q R 13 r (wherein M is a transition metal atom of group 9, 10, or 11; R 7’ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, or a neutral ligand coordinated to M; L 1 represents the ligand coordinated to M, and R 7’ and L 1 may be bonded to each other to form a ring. 13 represents a hydrocarbon group having 1 to 30 carbon atoms which may contain a hydrogen atom, a halogen atom, or a heteroatom; OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 8 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 9 ) 2M′ or an epoxy-containing group (where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium, x represents an integer of 0 to 3, and y represents an integer of 0 to 2. p is an integer of 1 or more, q is an integer of 1 or more, r is an integer of 0 or more, and p+q+r satisfies the valence of M.

[0077] In the present invention, M is a transition metal atom belonging to Group 9, 10, or 11 of the periodic table. M is preferably a nickel atom, palladium atom, or platinum atom of Group 10, a cobalt atom or rhodium atom of Group 9, or a copper atom of Group 11, more preferably a nickel atom, palladium atom, or platinum atom of Group 10, and most preferably a nickel atom or palladium atom of Group 10. The valence of M may be divalent. Here, the valence of M refers to the formal oxidation number used in organometallic chemistry. That is, it refers to the number of charges remaining on the atom of a certain element when the electron pair in the bond involving that element is assigned to an element with a higher electronegativity. For example, in the general formula [III] described below, E 1 is the phosphorus atom, X 1 is an oxygen atom, M is a nickel atom, R 7’ is a phenyl group, L 1 is pyridine, and the nickel atom forms bonds with the phosphorus atom, oxygen atom, carbon atom of the phenyl group, and nitrogen atom of the pyridine, the formal oxidation number of the nickel atom, i.e., the valence of the nickel atom, is 2. This is because, based on the definition above, in these bonds, electron pairs are assigned to the phosphorus atom, oxygen atom, carbon atom, and nitrogen atom, which are more electronegative than the nickel atom, and the charges are 0 for the phosphorus atom, -1 for the oxygen atom, -1 for the phenyl group, and 0 for the pyridine, and the complex is electrically neutral overall, so the remaining charge on the nickel atom is +2. As the divalent transition metal, for example, nickel (II), palladium (II), platinum (II), and cobalt (II) are preferable, and other than the divalent metal, copper (I) or rhodium (III) may also be used.

[0078] In the present invention, R 7’ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a neutral ligand coordinated to M. R 7’Specific examples of the alkyl group include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. In addition, when M is a nickel atom and a zero-valent transition metal compound, R 7’ R may be a neutral ligand coordinated to M. 7’ In the above, the neutral ligand coordinated to M is a neutral electron-donating ligand. One example is a ligand that is electrically neutral and can form a coordinate bond by coordinating an unpaired electron to the metal M. Examples include hydrocarbon compounds having 1 to 20 carbon atoms and containing a nitrogen atom, phosphorus atom, arsenic atom, oxygen atom, sulfur atom, selenium atom, or the like, which has an unpaired electron. Other examples include hydrocarbon compounds that may contain a heteroatom with a carbon-carbon unsaturated bond capable of coordinating to a transition metal, specifically compounds such as ethylene and cyclooctadiene, which form a π-donating bond by donating π electrons, and compounds such as dibenzylideneacetone (dba), which has an unsaturated bond and a heteroatom that coordinates to a metal. Examples of such compounds include known neutral ligands for metal complexes, such as acetonitrile, isonitrile, carbon monoxide, ethylene, and tetrahydrofuran, as well as π-electron-donating ligands such as allyl and cyclopentadienyl.

[0079] Ligand L in the present invention 1 is a hydrocarbon compound having 1 to 20 carbon atoms and having a nitrogen atom, phosphorus atom, arsenic atom, oxygen atom, sulfur atom, or selenium atom with an unpaired electron as an atom capable of forming a coordinate bond. 1 As L, a hydrocarbon compound which may contain a heteroatom having a carbon-carbon unsaturated bond capable of coordinating to a transition metal can also be used. 1 The number of carbon atoms in is 1 to 16, more preferably 1 to 10. L which forms a coordinate bond with M in the general formula [III] described later 1As the charge-sensitive material, a compound having no charge is preferred.

[0080] Preferred L in the present invention 1 Examples of the L include cyclic unsaturated hydrocarbons, phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, and amines. 1 Examples of the L include cyclic olefins, phosphines, pyridines, cyclic ethers, aliphatic esters, and aromatic esters. 1 As trialkylphosphines, pyridine, lutidine (dimethylpyridine), picoline (methylpyridine), R 9 CO2R 9 (R 9 The definition of is as described above. In addition, R 7’ and L 1 may be bonded to each other to form a ring. Examples of such a ring include 1,5-cyclooctadiene and the π-allyl bond shown in the following general formula [IV-1], which is also a preferred embodiment of the present invention. The π-allyl bond mode represented by the following general formula [IV-1] is represented by the general formula [IV], where M and R 7’ and L 1 Only the part where the two come together to form a π-allyl bond is shown.

[0081] [ka] [In formula [IV-1], where R 13 is as described above.]

[0082] In general formula [IV-1], R 13 As the alkyl group, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group are preferred.

[0083] In the general formula [IV], R 13 R may not be included, and when it is included, it represents a group that is substituted with the compound represented by the general formula [I] or [II] and does not remain in the metal complex that is the reaction product. 13 a hydrocarbon group having 1 to 30 carbon atoms which may contain a halogen atom or a heteroatom, OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 8 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x , OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 9 )2M' or the epoxy-containing group may be the same as described above.

[0084] Among the transition metal compounds that can be used, for example, transition metal compounds containing nickel atoms include bis(1,5-cyclooctadiene)nickel(0), represented by the general formula: Ni(CH2CR 13 The complex represented by the formula (where R 13 are as described above.], bis(cyclopentadienyl)nickel(II), general formula: Ni(CH2SiR 13 3) 2L 1 The complex represented by 2 (where R 13 , L 1 is as defined above), and the general formula: NiR 7’ 2L 1 The complex represented by 2 (where R 7’ , L 1is as described above.) etc. can be used.

[0085] Among these transition metal compounds, nickel(0)bis(1,5-cyclooctadiene), NiPhCl(PEt3)2 (hereinafter, Ph represents phenyl and Et represents ethyl), and NiPhCl(PPh3) 2、 NiPhCl(TMEDA) (hereinafter, TMEDA represents tetramethylethylenediamine), NiArBr(TMEDA) (where Ar = 4-fluorophenyl), Ni(acac) (hereinafter, acac represents acetylacetone), and compounds of the general formula: Ni(CHCR 13 The complex represented by the formula (where R 13 is as described above), general formula: Ni(CH2SiR 13 3) 2L 1 The complex represented by 2 (where R 13 , L 1 is as described above), and the general formula: NiR 7’ 2L 1 The complex represented by 2 (where R 7’ , L 1 are as defined above.), Pd(dba)2, Pd2(dba)3, Pd3(dba)4 (wherein dba represents dibenzylideneacetone), Pd(OCOCH3)2, (1,5-cyclooctadiene)Pd(methyl)(chloride). Particularly preferred are nickel(0) bis(1,5-cyclooctadiene), NiPhCl(PEt3)2, and NiPhCl(PPh3). 2、 NiPhCl(TMEDA), NiArBr(TMEDA), Ni(acac)2, Ni(CH2CHCH2)2, Ni(CH2CMeCH2)2, Ni(CH2SiMe3)2(Py)2 (hereinafter Py represents pyridine), Ni(CH2SiMe3)2(Lut)2 (hereinafter Lut represents 2,6-lutidine), NiPh2(Py)2, NiPh2(Lut)2, Pd(dba)2, Pd2(dba)3, Pd3(dba)4 (here, dba represents dibenzylideneacetone), Pd(OCOCH3)2, (1,5-cyclooctadiene)Pd(methyl)(chloride).

[0086] The reaction product of the present invention can be obtained by contacting a compound represented by the aforementioned general formula [I] or [II] with the aforementioned transition metal compound (referred to as [IV]), for example, in a molar ratio of [I] + [II]:[IV] = 1:99 to 99:1, in an organic solvent such as toluene or benzene at 0 to 100°C under reduced pressure to elevated pressure for 1 to 86,400 seconds. When a toluene or benzene solution of bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)2) is used as the transition metal compound, the generation of the reaction product can be confirmed by the change in color of the solution from yellow to, for example, red.

[0087] After this reaction, a portion of the components constituting the transition metal compound, other than the transition metal, is substituted with the portion excluding Z in general formula [I] or the compound of general formula [II], resulting in a metal complex, such as a metal complex represented by the following general formula [III], which is a reaction product of the compound represented by general formula [I] or [II] with the transition metal compound. This substitution reaction preferably proceeds quantitatively, but in some cases may not proceed completely. After completion of the reaction, other components derived from general formula [I], [II], and the transition metal compound may coexist in addition to the metal complex, such as the complex represented by general formula [III], which is a reaction product of the compound represented by general formula [I] or [II] with the transition metal compound. These other components may or may not be removed during the polymerization or copolymerization reaction of the present invention. Removal of these other components is generally preferred, as it results in higher activity.

[0088] It is believed that a metal complex represented by the following general formula [III] is contained in the reaction product of a compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table. Metal complex structures having a skeleton similar to that of the metal complex represented by the following general formula [III] have been reported as reaction products between a compound having a skeleton similar to that of the compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table, and it has been reported that these metal complexes exhibit catalytic activity (e.g., ACS Macro Lett. 2018, 7, 213-217, the aforementioned Non-Patent Document 3, and the aforementioned Non-Patent Document 4, etc.). Therefore, based on the reaction mechanism, it is believed that the reaction product of a compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table contains a metal complex represented by the following general formula [III]. As will be described later, a reaction product of a compound represented by the general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, 10, or 11 of the periodic table exhibits excellent catalytic activity, and therefore, a structure represented by the following general formula [III], which is estimated from the reaction mechanism, is presumed to be one of the compounds exhibiting catalytic activity. However, as mentioned above, the structure of the metal complex that is the reaction product is not limited to the structure represented by general formula [III].

[0089] In addition, when producing a metal complex represented by the following general formula [III], when the compound represented by the general formula [I] or [II] is reacted with a transition metal compound containing a transition metal belonging to Group 9, Group 10 or Group 11 of the periodic table, a coordination compound (L 1 ) and R in general formula [III] 7 A covalent compound for substituting may be present. When a nickel atom or a palladium atom is used as M in the present invention, the stability of the generated metal complex may be increased by allowing a Lewis basic coordinating compound to coexist in the system. In such cases, the coexistence of the coordinating compound may be allowed as long as the coordinating compound does not inhibit the polymerization reaction or copolymerization reaction of the present invention. The coordinating compound used in the present invention may be a hydrocarbon compound having 1 to 20 carbon atoms and containing an oxygen atom, a nitrogen atom, a phosphorus atom, an arsenic atom, a sulfur atom, or a selenium atom as an atom capable of forming a coordinate bond, or a hydrocarbon compound which may contain a heteroatom having a carbon-carbon unsaturated bond capable of coordinating to a transition metal, and the L 1 It may be synonymous with:

[0090] The covalent compound used in the present invention is a compound in which a ligand derived from a transition metal compound is bonded to R in the general formula [III]. 7 R is a compound that can be substituted with R and may be an organometallic compound. 7 is incorporated into the polymer as the initiation terminal of the polymerization reaction and can significantly contribute to the initial rate of the polymerization reaction. 7 It is also preferable to use a covalent compound for introducing the following. The covalent bond compound may be an organolithium compound, and R 7 Li (where R 7 may be a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom), or an organolithium compound having a hydrocarbon group having 1 to 10 carbon atoms. Examples of organolithium compounds having a hydrocarbon group having 1 to 10 carbon atoms include methyllithium, n-butyllithium, and phenyllithium. Of these, methyllithium and phenyllithium are preferred, and methyllithium is more preferred.

[0091] The metal complex of the present invention is a metal complex represented by the following general formula [III]:

[0092] [ka]

[0093] [R in general formula [III] 1 ~R 7 , E 1 , X 1 , M, L 1 is as follows: R 1 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms. 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 atoms (iii) A linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of heteroatoms and groups containing heteroatoms. (iv) OR 9 , CO2R 9 , CO2M', C(O)N(R 8 )2, C(O)R 9 ,OC(O)R 9 , S.R. 9 , SO2R 9 , SOR 9 , OSO2R 9 , P(O)(OR 9 ) 2-y (R 8 ) y , CN, NHR 9 , N(R 9 )2, Si(OR 8 ) 3-x (R 8 ) x, OSi(OR 8 ) 3-x (R 8 ) x , NO2, SO3M', PO3M'2, P(O)(OR 8 )2M', or an epoxy-containing group, where R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 represents a hydrocarbon group having 1 to 20 carbon atoms. M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium; x represents an integer of 0 to 3; and y represents an integer of 0 to 2. R 2 , R 3 and R 4 Adjacent 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 an oxygen atom, a nitrogen atom, and a sulfur atom, in which case the ring has 5 to 8 members and may or may not have a substituent on the ring. R 5 or R 6 each independently represents a fused polycyclic hydrocarbon group which may have a substituent. E 1 represents a phosphorus atom, an arsenic atom, or an antimony atom. X 1 represents an oxygen atom, a sulfur atom, or SO3. M represents a transition metal atom belonging to Group 9, 10 or 11 of the periodic table. R 7 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L 1 represents a ligand coordinated to M. R 7 and L 1 may be bonded to each other to form a ring.

[0094] In the general formula [III], R 1 ~R 6 , E 1 , X 1As described above, between the metal complex in the reaction product and the metal complex represented by the general formula [III], there is a main skeleton containing a benzene ring and these substituents (R 1 ~R 6 , E 1 , X 1 ) The complex structures have commonality in this respect. In addition, M and L in the general formula [III] 1 is as explained in the transition metal compound.

[0095] In the present invention, R 7 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. R in zero-valent transition metal compounds where M is Ni 7’ may be a neutral ligand coordinated to M, but when a compound represented by the general formula [I] or [II] reacts with a transition metal compound in which M is Ni and has a valence of 0, Ni becomes divalent, and therefore, R after the reaction 7 becomes an anionic ligand, not a neutral ligand. For example, when a compound represented by the general formula [I] or [II] reacts with nickel(0)bis(1,5-cyclooctadiene), the ligand derived from the transition metal compound becomes an anionic ligand, R 7 and L 1 are bonded to each other to form a ring, forming a cycloocten-1-yl group. The polymerization or copolymerization reaction in the present invention is carried out by reacting M and R 7 It is believed that the reaction is initiated by the insertion of an olefin such as propylene or a copolymerizable monomer thereof into the bond of R 7 If the number of carbon atoms in R is too large, this initiation reaction tends to be inhibited. 7 The group preferably has 1 to 16 carbon atoms, excluding the carbon atoms contained in the substituent, and more preferably has 1 to 10 carbon atoms. R 7Specific examples of the alkyl group include a hydride group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenyl group, a p-methylphenyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. In addition, R 7 and L 1 may be bonded to each other to form a ring. Examples of such a ring include a cycloocten-1-yl group and an acetylacetonate group, which is also a preferred embodiment of the present invention.

[0096] Specific combinations of substituents and the like in the general formula [III] in the present invention are shown in the following Table 2. However, the specific examples are not limited to the following examples.

[0097] [Table 3]

[0098] [Table 4] In Tables 3 and 4, 1,4,5-η-COE represents a (1,4,5-η)-4-cycloocten-1-yl group.

[0099] Further, compounds in which the central metal M of the compounds of Complex Nos. 1 to 41 exemplified in Table 2 is replaced with Pd instead of Ni are also exemplified.

[0100] In the present invention, the reaction may be carried out in advance in a vessel separate from the reactor used for the polymerization of an olefin such as propylene or the copolymerization of an olefin with a (meth)acrylic acid ester. The resulting metal complex, which is the reaction product of the compound represented by general formula [I] or [II] and a transition metal compound, may then be subjected to the polymerization of an olefin such as propylene or the copolymerization of an olefin with a (meth)acrylic acid ester. Alternatively, the reaction may be carried out in the presence of these monomers. The reaction may also be carried out in the reactor used for the polymerization of an olefin such as propylene or the copolymerization of an olefin with a (meth)acrylic acid ester. In this case, these monomers may or may not be present. Furthermore, the compounds represented by general formulas [I] and [II] may each be used alone, or multiple components may be used in combination. Such a combination of multiple components is particularly useful for broadening the molecular weight distribution and comonomer content distribution.

[0101] As described above, the metal complex of the present invention, i.e., the metal complex represented by general formula [III], which is a reaction product between the compound represented by general formula [I] or [II] and the transition metal compound containing a transition metal belonging to Group 9, Group 10, or Group 11 of the periodic table, can be produced by contacting the compound represented by general formula [I] or [II] with a transition metal compound containing a transition metal belonging to Group 9, Group 10, or Group 11 of the periodic table, and, if necessary, further reacting them using the coordination compound or the covalent compound.

[0102] 2. Olefin polymerization catalyst components The catalyst component for olefin polymerization of the present invention is characterized by containing the metal complex of the present invention. In the present invention, the metal complex of the present invention can be used as a catalyst component for the polymerization or copolymerization of olefins. As described above, the metal complex of the present invention can be produced by reacting a compound represented by general formula [I] or [II] with a transition metal compound. When the metal complex of the present invention is used as a catalyst component, it may be used as a reaction solution as is, isolated, or supported on a carrier. Supporting on a carrier may be carried out in a reactor used for the polymerization of olefins or the copolymerization of olefins and (meth)acrylic acid esters, in the presence or absence of these monomers, or may be carried out in a vessel separate from the reactor.

[0103] Any carrier can be used as long as it does not impair the spirit and scope of the present invention. Generally, inorganic oxides and polymer carriers are suitable. Specific examples include SiO2, Al2O3, MgO, ZrO2, TiO2, BO3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof. Mixed oxides such as SiO2-Al2O3, SiO2-VO5, SiO2-TiO2, SiO2-MgO, and SiO2-Cr2O3 can also be used. 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 also be used. There are no particular limitations on the particle size, particle size distribution, pore volume, or specific surface area of ​​these carriers, and any carrier can be used.

[0104] Examples of inorganic silicates that can be used include clay, clay minerals, zeolites, and diatomaceous earth. These may be synthetic products or naturally occurring minerals. Specific examples of clay and clay minerals include allophane-based minerals such as allophane, kaolinite-based minerals such as dickite, nacrite, kaolinite, and anoxicite, halloysite-based minerals such as metahaloysite and halloysite, serpentine-based minerals such as chrysotile, lisardite, and antigorite, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and glauconite, attapulgite, sepiolite, pyrogorskite, bentonite, kibushi clay, gairome clay, hisingerite, pyrophyllite, and ryokudeite. These may form a mixed layer. Examples of artificial synthetic materials include synthetic mica, synthetic hectorite, synthetic saponite, synthetic taeniolite, etc. Among these specific examples, preferred are kaolin group materials such as dickite, nacrite, kaolinite, and anoxite, halloysite group materials such as metahaloysite and halloysite, serpentine group materials such as chrysotile, lisaldite, and antigorite, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and glauconite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite, and particularly preferred are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite.

[0105] These supports may be used as is, 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 also be performed.

[0106] 3. Olefin polymerization catalysts The olefin polymerization catalyst of the present invention is characterized by containing the following components (A) and (B): Component (A): the metal complex of the present invention Component (B): Organoaluminum compound

[0107] 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.

[0108] 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.

[0109] Among these, triisobutylaluminum or tri-normal-octylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination. The aluminum compounds may be modified with alcohol, phenol, or the like. Examples of such modifying agents include methanol, ethanol, 1-propanol, isopropanol, butanol, phenol, 2,6-dimethylphenol, and 2,6-di-t-butylphenol, with 2,6-dimethylphenol and 2,6-di-t-butylphenol being preferred.

[0110] In the method for preparing the olefin polymerization catalyst according to the present invention, the method for contacting component (A) and component (B) is not particularly limited. The contacting may be carried out not only during catalyst preparation but also during prepolymerization with an olefin or during olefin polymerization. The contact of the above components (A) and (B) is preferably carried out in an inert gas such as nitrogen, in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, etc. The contact can be carried out at a temperature between −20° C. and the boiling point of the solvent, and is particularly preferably carried out at a temperature between room temperature and the boiling point of the solvent.

[0111] 4. Olefin polymer manufacturing method 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 olefin polymerization catalyst of the present invention. The olefin in the present invention has the general formula: CH═CHR 10 where R 10 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. 10 If the carbon number of R is more than 20, sufficient polymerization activity tends not to be exhibited. 10 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, it is particularly preferred that the olefin is propylene.

[0112] 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 polymerization catalyst.

[0113] The (meth)acrylic acid ester monomer in the present invention is represented by the general formula: CH═C(R 11 )CO2(R 12 ) where R 11 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may have a branched, cyclic, and / or unsaturated bond. 12 is a hydrocarbon group having 1 to 30 carbon atoms, which may have a branched, cyclic, and / or unsaturated bond. 12 It may contain a heteroatom at any position within the group. R 11 If the carbon number of R is 11 or more, sufficient polymerization activity tends not to be exhibited. 11 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and preferred (meth)acrylic acid esters include those 11 is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. More preferred (meth)acrylic acid ester monomers include those in which R 11 is a methyl group or a methacrylate ester R 11 acrylate esters in which R is a hydrogen atom. 12 If the carbon number of R exceeds 30, the polymerization activity tends to decrease. 12The carbon number of R is 1 to 30. 12 preferably has 1 to 12 carbon atoms, and more preferably has 1 to 8 carbon atoms. Also, R 12 Examples of heteroatoms that may be contained within R include oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, nitrogen atoms, silicon atoms, fluorine atoms, and boron atoms. Among these heteroatoms, oxygen atoms, silicon atoms, and fluorine atoms are preferred, and oxygen atoms are more preferred. 12 It is also preferred that the group does not contain a heteroatom.

[0114] More preferred (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. , hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene oxide (meth)acrylate, trifluoromethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. A single (meth)acrylic acid ester may be used, or multiple (meth)acrylic acid esters may be used in combination.

[0115] 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 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, or the like. Specific examples include 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. Among these, 3-buten-1-ol, ethyl 10-undecenoate, and 10-undecen-1-ol are particularly preferred.

[0116] Examples of the allyl monomer in the present invention include an allyl monomer (propenyl monomer) having 3 carbon atoms and an allyl-based monomer having 4 or more carbon atoms and having an allyl group. The allyl monomer is an allyl monomer having a polar group containing a halogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, or the like, 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, or the like. Preferred 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, and diallyl ether. Among these, allyl acetate and allyl alcohol are particularly preferred, and allyl acetate, allyl ether, and diallyl ether are more preferred.

[0117] The polymerization reaction of the present invention is carried out in the presence or absence of a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, or methylcyclohexane, a liquid such as a liquefied α-olefin, or a polar solvent such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, or ethylene glycol. A mixture of the liquid compounds described herein may also be used as the solvent. Furthermore, an ionic liquid may also be used as the solvent. The aforementioned hydrocarbon solvents and ionic liquids are more preferred for achieving high polymerization activity and high molecular weight.

[0118] In the present invention, the polymerization reaction can be carried out in the presence or absence of known additives. Preferred additives include polymerization inhibitors that inhibit radical polymerization and additives that stabilize the resulting copolymer. Examples of preferred additives include quinone derivatives and hindered phenol derivatives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction products of trimethylaluminum and BHT, and reaction products of tetravalent titanium alkoxide and BHT can be used. Furthermore, inorganic and / or organic fillers can be used as additives, and polymerization can be carried out in the presence of these fillers. Furthermore, the L of the present invention can be used in the present invention. 1 An ionic liquid may be used as an additive.

[0119] A preferred additive in the present invention is a Lewis base. By selecting an appropriate Lewis base, the activity, molecular weight, and copolymerizability of the acrylic ester can be improved. The amount of the Lewis base is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, and more preferably 0.3 to 30 equivalents, relative to the transition metal M in the catalyst component present in the polymerization system. There are no particular limitations on the method for adding the Lewis base to the polymerization system, and any method can be used. For example, the Lewis base may be added by mixing it with the catalyst component of the present invention, or by mixing it with the monomer, or may be added to the polymerization system independently of the catalyst component or the monomer. Furthermore, multiple Lewis bases may be used in combination. Furthermore, the Lewis base of the present invention can be added by mixing it with the monomer, or by mixing it with the catalyst component or the monomer. 1 The Lewis base used may be the same as or different from the above.

[0120] Examples of Lewis bases include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitriles, arylnitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons. Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, and particularly preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, and furan derivatives.

[0121] Specific Lewis base compounds include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, and 1,8-diazabicyclo-[5.4.0]-undec-7-ene. , 1,4-diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, picoline, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrrolidinophosphine, tris(pyrrolidino)borane, and the like.

[0122] In the present invention, there are no particular limitations on the polymerization method. Examples of preferred methods include slurry polymerization, in which at least a portion of the polymer produced forms a slurry in a medium; bulk polymerization, in which liquefied monomer itself is used as the medium; gas-phase polymerization, in which vaporized monomer is used; and high-pressure ionic polymerization, in which at least a portion of the polymer produced is dissolved in liquefied monomer at high temperature and pressure. Batch polymerization, semi-batch polymerization, and continuous polymerization are also acceptable. Living polymerization may also be used, and polymerization may be carried out while chain transfer occurs. Furthermore, a so-called chain transfer agent (CSA) may also be used to carry out chain shuttling or coordinated chain transfer polymerization (CCTP).

[0123] The unreacted monomers and the medium may be separated from the resulting copolymer and recycled for reuse. When recycling, these monomers and medium may be reused after purification or without purification. The resulting copolymer can be separated from the unreacted monomers and medium by a conventional method, such as filtration, centrifugation, solvent extraction, or reprecipitation using a poor solvent. There are no particular limitations on the polymerization temperature, polymerization pressure, and polymerization time, but they can usually be optimally set within the following ranges, taking productivity and process capacity into consideration: 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, preferably 0.5 minutes to 7 hours, and more preferably 1 minute to 6 hours.

[0124] In the present invention, 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. Note that a small amount of oxygen or air may be present. There are no particular limitations 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 then the catalyst is supplied thereto. In this case, additional monomer or additional catalyst may be supplied to the polymerization reactor. Furthermore, in the case of continuous polymerization, a method can be used in which predetermined amounts of monomer and catalyst are supplied to the polymerization reactor continuously or intermittently and the polymerization reaction is carried out continuously.

[0125] Regarding the control of the copolymer composition, a method of controlling by feeding a plurality of monomers to a reactor and changing the feeding ratio can be generally used. Other methods include a method of controlling the copolymer composition by utilizing differences in the monomer reactivity ratio due to differences 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. Examples of such methods include controlling the molecular weight by controlling the polymerization temperature, controlling the monomer concentration, using a chain transfer agent, and controlling the molecular weight by controlling the ligand structure in a transition metal complex. When a chain transfer agent is used, any conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used.

[0126] In particular, the copolymer obtained by the present invention with a polar group-containing monomer exhibits excellent coating properties, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibilization with other resins due to the effects of the polar groups of the copolymer. Utilizing these properties, the copolymer of the present invention can be used in a variety of applications. For example, it can be used as a film, sheet, adhesive resin, binder, compatibilizer, wax, etc. [Example]

[0127] 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 dehydrated and deoxygenated solvents were used. The abbreviations used in the description are as follows: nBu: normal butyl group, iBu: isobutyl group, tBu: tertiary butyl group iPr: isopropyl group, Me: methyl group, Et: ethyl group, Ph: phenyl group OMOM: methoxymethoxy group (-OCH2OCH3) AcOH: acetic acid, EtOAc: ethyl acetate, THF: tetrahydrofuran, DMF: dimethylformamide dba: dibenzylidene acetone

[0128] 1. Evaluation method (1) The weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn were determined by the following GPC measurement. First, approximately 20 mg of sample was placed in a vial for a Polymer Laboratory high-temperature GPC pretreatment device, PLSP260VS. o-Dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L) was added to adjust the polymer concentration to 0.1% by mass. The polymer was dissolved by heating to 135°C in the PL-SP 260VS high-temperature GPC pretreatment device and filtered through a glass filter to prepare a sample. Note that no polymer was trapped on the glass filter during the GPC measurement in this invention. Next, GPC measurement was performed using a Waters GPCV 2000 equipped with a Tosoh TSKgel GMH-HT column (30 cm x 4 columns) and an RI detector. The measurement conditions were as follows: sample solution injection volume: approximately 520 μL, column temperature: 135°C, solvent: o-Dichlorobenzene, and 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 retention time to molecular weight was created from the viscosity equation of the polystyrene standard sample and the ethylene-based polymer, and the molecular weight was calculated based on the calibration curve. The viscosity equation used was [η] = K × Mα, where K = 1.38E-4 and α = 0.70 for polystyrene and K = 1.03E-4 and α = 0.78 for the propylene-based polymer.

[0129] (2) Comonomer content in copolymer: Determined by the following IR analysis. The comonomer content (mol%) was determined by IR measurement of a sample formed into a sheet by heat pressing using a Shimadzu FTIR-8700. In this case, in the case of acrylic esters, the comonomer content was determined by IR measurement of 1,740 cm -1 / 730-720cm -1 The area ratio is converted using the following formula: [Acrylate]=1.276(area ratio)-0.0434

[0130] 2. Ligand synthesis (Synthesis Example 1): Synthesis of Ligand B-482 Ligand B-482 was synthesized according to the following scheme.

[0131] [ka]

[0132] (i) Synthesis of Compounds 2 and 4 Synthesized according to JP 2019-172983. (ii) Synthesis of Compound 5 Compound 4 (1.0 g, 3.35 mmol) in THF (20 mL) n BuLi (2.5 M, 1.47 mL) was added at 0 °C and stirred at 25 °C for 2 h. After cooling to -78 °C and stirring for 30 min, PCl (1.38 g, 10.05 mmol) was added to the solution at -78 °C and stirred at 25 °C for 1 h to give a yellow suspension. The solution was concentrated to give an oily yellow liquid. This mixture was used in the next reaction without further purification.

[0133] (iii) Synthesis of Compound 7 Compound 6 (5.0 g, 30.08 mmol) in THF (80 mL) n BuLi (2.5 M, 13.24 mL) was added dropwise at −78° C., and the mixture was heated to 25° C. and stirred for 2 hours. A solution of compound 5 (6.01 g, 15.04 mmol) in THF (30 mL) was added dropwise at -78 °C and stirred at 25 °C for 14 h to give a yellow suspension. BH3-Me2S (10 M, 9.02 mL) was added dropwise at 0 °C and stirred at 25 °C for 16 h to give a yellow suspension. The solution was concentrated to give a yellow solid. The yellow solid was washed with hexane (40 mL) to give compound 7 (7.0 g, 7.91 mmol, 26%) as a white solid.

[0134] (iv) Synthesis of Ligand B-482 To a solution of compound 7 (2.2 g, 3.27 mmol) in dichloromethane (5 mL), HCl / EtOAc (10 M, 100 mL) was added at 20°C, and the mixture was stirred at 20°C for 2 hours to obtain a colorless solution. After the solvent was removed under reduced pressure, NaHCO3 (100 mL) was added to adjust the pH to 6.5-7.0, and the mixture was extracted with dichloromethane (80 mL x 2). The solvent was removed under reduced pressure to obtain a white solid. The solid was washed with hexane (15 mL x 2) and Et2O (15 mL x 2), and B-482 (0.85 g, 1.38 mmol, 42%) was obtained as a white solid. The obtained B-482 1 HNMR and 31 The results of PNMR measurement are shown below. 1 HNMR(CDCl3,δ,ppm):7.84(m,6H),7.42(m,4H),7.32(m,3H),7.25(m,3H),7.11(d,2H),6.85(d,1 H),6.50(t,1H),6.44(br,1H),5.87(d,1H),5.21(s,2H),2.14(m,2H),0.979(d,6H),0.896(d,6H) 31 PNMR (CDCl3, δ, ppm): -24.0 (s).

[0135] (Synthesis Example 2): Synthesis of Ligand B-504 Ligand B-504 was synthesized according to the following scheme.

[0136] [ka]

[0137] (i) Synthesis of Compound 9 A solution of compound 8 (2.0 g, 7.13 mmol), HIO (650.22 mg, 2.85 mmol), and I (1.45 g, 5.71 mmol) in AcOH (10 mL) was added with HO (1.28 mL, 71.31 mmol) and HSO (499.60 mg, 4.99 mmol) at 20 °C, stirred, and heated at 75 °C for 20 h to give a black solution. The solution was poured into ice water and extracted with ethyl acetate (150 mL x 2). The organic layer was washed with NaSO, water, and brine, dried over NaSO, filtered, and concentrated to give a bright yellow oil. Isolation by silica gel chromatography gave compound 9 (2.2 g, 4.13 mmol, 58%) as a white solid.

[0138] (ii) Synthesis of Compound 10 PPh3 (394.24 mg, 1.50 mmol), NiCl2(PPh3)2 (122.91 mg, 187.89 μmol), and Zn (368.58 mg, 5.64 mmol) were weighed into a reaction vessel and added to DMF (20 mL). The solution was stirred at 70 °C for 1 h, and then a solution of compound 9 (1.0 g, 1.88 mmol) in DMF (20 mL) was slowly added dropwise. The mixture was stirred at 70 °C for 24 h, resulting in a black suspension. The mixture was further stirred at 20 °C for 12 h, resulting in a gray suspension. HCl (1 M, 30 mL) was added, and the mixture was extracted with ethyl acetate (50 mL × 2). The organic layer was washed with water and brine, dried over Na2SO4, filtered, and the solvent was evaporated. Isolation by silica gel chromatography afforded compound 10 (0.05 g, 111.34 μmol) as a pale yellow liquid.

[0139] (iii) Synthesis of Compound 11 To a solution of compound 10 (4.0 g, 14.37 mmol) in THF (50 mL), nBuLi (2.5 M, 6.32 mL) was added at -78 °C and stirred at 25 °C for 2 hours. After cooling to -78 °C, a solution of compound 5 (2.87 g, 7.18 mmol) in THF (20 mL) was added dropwise and stirred at 25 °C for 12 hours to give a yellow suspension. The solution was concentrated to give a yellow oily liquid. The solid was isolated by silica gel column chromatography and washed with hexane (40 mL × 2), giving compound 11 (1.7 g, 1.92 mmol, 27%) as a white solid.

[0140] (iV) Synthesis of Ligand B-504 To a solution of compound 11 (1.6 g, 1.81 mmol) in dichloromethane (1.0 mL), HCl / EtOAc (4 M, 130 mL) was added at 0°C and stirred at 20°C for 2 hours to obtain a pale yellow solution. After the solvent was removed by evaporation under reduced pressure, NaHCO3 (500 mL) was added to adjust the pH to 6.5-7.0, followed by extraction with dichloromethane (150 mL x 2). The organic layer was removed by evaporation under reduced pressure to obtain B-504 (1.5 g, 1.79 mmol, 99%) as a pale yellow solid. 1 HNMR and 31 The results of PNMR measurement are shown below. 1 HNMR(CDCl3,δ,ppm):7.90(s,2H),7.86(s,2H),7.74(br,2H),7.30(m,6H),7.14(d,2H),6.93(d,1H),6.69(m,1 H),6.56(t,1H),6.26(d,1H),5.18(s,2H),2.40(m,2H),1.47(s,18H),1.43(s,18H),1.06(d,6H),0.865(d,6H) 31 PNMR (CDCl3, δ, ppm): -29.0 (s).

[0141] (Comparative Synthesis Example 1): Synthesis of Ligand B-549 Ligand B-549 was synthesized according to the following scheme.

[0142] [ka]

[0143] (i) Synthesis of Compound 13 To a solution of compound 12 (2.25 g, 13.29 mmol) in THF (20 mL), nBuLi (2.5 M, 5.62 mL) was added at 0 °C and stirred at 20 °C for 2.5 hours. To a solution of compound 5 (5.35 g, 13.39 mmol) in THF (20 mL), nBuLi (2.5 M, 5.62 mL) was added dropwise at -78 °C and stirred at 20 °C for 2 hours to obtain a yellow solution. This reaction solution was used in the next reaction without purification.

[0144] (ii) Synthesis of Compound 14 To a solution of compound 6 (2.23 g, 13.39 mmol) in THF (30 mL), nBuLi (2.5 M, 5.89 mL) was added at -78°C, and the mixture was stirred at 20°C for 2 hours. A solution of compound 13 (7.11 g, 13.39 mmol) in THF (40 mL) was added, and the mixture was stirred at 20°C for 12 hours to obtain a yellow suspension. The solution was concentrated to obtain a gummy yellow solid. Compound 14 (4.85 g, 7.34 mmol, 55%) was isolated by silica gel chromatography to obtain a white solid. 1 HNMR and 31 The results of PNMR measurement are shown below.

[0145] (iii) Synthesis of B-549 To a solution of compound 14 (4.65 g, 7.04 mmol) in dichloromethane (10 mL), HCl / EtOAc (4 M, 80 mL) was added at 0°C and stirred at 20°C for 2 hours to obtain a colorless solution. After the solvent was removed under reduced pressure, NaHCO3 (300 mL) was added to adjust the pH to 6.5-7.0, followed by extraction with dichloromethane (100 mL). The organic layer was removed under reduced pressure to obtain a white solid. The solid was washed with dichloromethane / hexane (1:20, 10 mL) to obtain B-549 (3.0 g). 1 The results of HNMR measurement are shown below. 1HNMR(CDCl3,δ,ppm):8.12(m,1H),7.82(m,2H),7.34(m,3H),7.21(m,4H),7.06(m,3H),6.75(d,1H),6.73(d,1H),6.20(d, 2H),6.02(s,1H),3.88(s,3H),3.81(s,6H),2.73(m,1H),2.55(m,1H),1.17(d,3H),1.08(d,3H),1.06(d,3H),1.00(d,3H) 31 PNMR(CDCl3, δ, ppm): -49.8(s).

[0146] (Synthesis Example 3): Synthesis of Ligand X-146 Ligand X-146 was synthesized according to the following scheme.

[0147] [ka]

[0148] (i) Synthesis of Compounds 2 and 4 Synthesized according to JP 2019-172983. (ii) Synthesis of Compound 5 Compound 4 (1.0 g, 3.35 mmol) in THF (20 mL) n BuLi (2.5 M, 1.47 mL) was added at 0 °C and stirred at 25 °C for 2 h. After cooling to -78 °C and stirring for 30 min, PCl (1.38 g, 10.05 mmol) was added to the solution at -78 °C and stirred at 25 °C for 1 h to give a yellow suspension. The solution was concentrated to give an oily yellow liquid. This mixture was used in the next reaction without further purification.

[0149] (iii) Synthesis of compound 16 To a solution of compound 15 (6.0 g, 33.29 mmol) in THF (100 mL) n BuLi (2.5 M, 14.65 mL) was added dropwise at −78° C., and the mixture was stirred at −78° C. for 2 hours. A solution of compound 5 (6.65 g, 16.64 mmol) in THF (50 mL) was added dropwise at -78 °C and stirred at 20 °C for 16 h to give a yellow suspension. The reaction was slowly quenched with water (250 mL), extracted with ethyl acetate (250 mL × 3), dried over NaSO, filtered, and the solvent was evaporated. Silica gel chromatography afforded compound 16 as a white solid.

[0150] (iv) Synthesis of Ligand X-146 A solution of compound 16 (700 mg, 1.02 mmol) in dichloromethane (10 mL) was added with HCl / EtOAc (4 M, 10.19 mL) at 0 °C and stirred at 20 °C for 16 h to obtain a colorless solution. After removing the solvent under reduced pressure, NaHCO (100 mL) was added to adjust the pH to 6.5-7.0, and the mixture was extracted with dichloromethane (80 mL × 2). The solvent was removed under reduced pressure to obtain a white solid. The solid was washed with hexane (15 mL × 2) and EtO (15 mL × 2) to obtain X-146 as a white solid. The resulting X-146 1 HNMR and 31 The results of PNMR measurement are shown below. 1 HNMR(CDCl3,δ,ppm):0.930(br,12H),2.09(br,2H),3.51(m,2H),3.67(m,2H),4.85(br,1H),6.62(m,1H),6.60-7.09(m,22H). 31 PNMR (CDCl3, δ, ppm): -27.1 (s).

[0151] 3. Polymerization Evaluation Example 1: Homopolymerization of propylene using ligand B-482 (i) Synthesis of metal complexes All of the following operations were carried out under a nitrogen atmosphere. Hereinafter, bis-1,5-cyclooctadiene nickel(0) will be referred to as Ni(COD)2. Ni(COD)2 (70.8 mg, 0.257 mmol) was weighed into a two-necked recovery flask, and toluene (12.85 mL) was added to prepare a 0.02 mmol / mL solution. 6.95 mL of this Ni(COD)2 toluene solution was added to the two-necked recovery flask containing B-482 (85.8 mg, 0.139 mmol) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 30 minutes. The color of the reaction solution changed from yellow to orange. A 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2 ((B-482)Ni((1,4,5-η)-COE)) was obtained. The concentration of the reaction product was calculated assuming that B-482 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0152] (ii) Homopolymerization of propylene Tri-n-octylaluminum (0.1 mmol) was introduced into a 2 L induction-stirred autoclave. After propylene (500 mL) was added to the autoclave, a 0.02 mmol / mL solution (5.0 mL) of the reaction product of B-482 and Ni(COD)2 obtained in (i) above was added. 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 (g) per mole of complex used in the polymerization. The GPC results for the obtained polymer are also shown in Table 5. The activity was calculated assuming that the ligand B-482 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0153] Example 2: Homopolymerization of propylene using ligand B-504 (i) Synthesis of metal complexes A complex was synthesized in the same manner as in Example 1(i), except that B-504 (87.4 mg, 0.104 mmol) obtained in Synthesis Example 2 was used as the ligand and 5.2 mL of a toluene solution of Ni(COD)2 (0.02 mmol / mL) was used, to obtain a 0.02 mmol / mL solution of the reaction product of B-504 and Ni(COD)2 ((B-504)Ni((1,4,5-η)-COE)). The concentration of the reaction product was calculated assuming that B-504 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0154] (ii) Homopolymerization of propylene Polymerization was carried out in the same manner as in Example 1(ii), except that 5.2 mL of a 0.02 mmol / mL solution of the reaction product of B-504 and Ni(COD)2 obtained in (i) above ((B-504)Ni((1,4,5-η)-COE)) was used instead of the 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2. The results are shown in Table 5. The activity was calculated assuming that the ligand B-504 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0155] Example 3: Copolymerization of propylene and ethyl 10-undecenoate using ligand B-482 (i) Synthesis of metal complexes A complex was synthesized in the same manner as in Example 1(i), except that B-482 (80.2 mg, 0.130 mmol) obtained in Synthesis Example 1 was used as the ligand and 6.5 mL of a toluene solution of Ni(COD)2 (0.02 mmol / mL) was used, to obtain a 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2 ((B-482)Ni((1,4,5-η)-COE)). The concentration of the reaction product was calculated assuming that B-482 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0156] (ii) Copolymerization of propylene and ethyl 10-undecenoate Polymerization was carried out in the same manner as in Example 1(ii), except that 5.0 mL of the 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2 obtained in (i) above ((B-482)Ni((1,4,5-η)-COE)) and ethyl 10-undecenoate (12 mL, 50 mmol) were used. The results are shown in Table 5. The activity was calculated assuming that the ligand B-482 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0157] (Comparative Example 1): Homopolymerization of propylene using ligand B-549 (i) Synthesis of comparative metal complexes A complex was synthesized in the same manner as in Example 1, except that B-549 (51.6 mg, 0.187 mmol) obtained in Comparative Synthesis Example 1 was used as the ligand and 9.35 mL of a toluene solution of Ni(COD)2 (0.02 mmol / mL) was used, to obtain a 0.02 mmol / mL solution of the reaction product of B-549 and Ni(COD)2 ((B-549)Ni((1,4,5-η)-COE)). The concentration of the reaction product was calculated assuming that B-549 and Ni(COD)2 reacted in a 1:1 ratio to form a nickel complex.

[0158] (ii) Homopolymerization of propylene Polymerization was carried out in the same manner as in Example 1(ii), except that 5.0 mL of the solution of the reaction product ((B-549)Ni((1,4,5-η)-COE)) (0.02 mmol / mL) of B-549 and Ni(COD) obtained in (i) above was used. The results are shown in Table 5. The activity was calculated assuming that the ligand B-549 and Ni(COD) reacted in a 1:1 ratio to form a nickel complex.

[0159] (Example 4): (B-482) Homopolymerization of Propylene Using NiMePy (i) Synthesis of metal complexes (B-482)NiMePy was synthesized according to the following scheme.

[0160] [ka]

[0161] All operations were carried out under a nitrogen atmosphere. Dehydrated solvents were used. Nickel chloride hexahydrate (0.51 g, 2.1 mmol) was placed in a 100 mL two-necked eggplant flask, and pyridine (2.0 mL, 25.8 mmol) was added at room temperature. The mixture was stirred at 40 °C for 30 minutes. The reaction mixture instantly changed color from green to turquoise. The volatile components of the reaction mixture were then removed under reduced pressure to obtain NiCl2Py4. A toluene / THF solution (9 / 1 vol%, 20 mL) and pyridine (1.0 mL, 12.9 mmol) were added to the mixture, and the mixture was stirred at 0 °C for 15 minutes to prepare a slurry solution. A solution of methyllithium in diethyl ether (1.09 mol / L, 3.9 mL, 4.3 mmol) was slowly added to the mixture. The solution changed color from yellowish brown to reddish brown. Then, a toluene solution (20 mL) of B-482 (902.9 mg, 1.47 mmol) was quickly added dropwise via cannula at 0°C, and the mixture was heated to 40°C and stirred for 1 hour. The reaction solution remained reddish-brown, but the color slightly lightened. The reaction solution was then filtered through Celite, and the filtrate was concentrated. Hexane (10 mL) was added, and the mixture was cooled to 0°C. The precipitated solid was collected. The resulting solid was then redissolved in toluene (30 mL), the insoluble matter was filtered, and the filtrate was concentrated to obtain (B-482)NiMePy (0.518 g, 45% yield). The obtained (B-482)NiMePy 1 HNMR and 31 The results of PNMR measurement are shown below. 1 HNMR(C6D6,23℃,δ):-1.23(d,J=5.40Hz,3H),0.93(br,6H),1.12(br,6H),2.38-2.85(br,2H),5.20(s,1H),5.23(s,1H),6.07( t,J=7.83Hz,1H),6.18(t,J=7.02Hz,1H),6.47-6.63(br,1H),6.86(d,J=7.55Hz,1H),7.11-7.35(m,19H),7.65-7.74(br,4H). 31 PNMR(C6D6,23℃,δ):42.6(s,1P).

[0162] Toluene (8 mL) was added to a two-necked recovery flask containing the obtained (B-482)NiMePy (76.5 mg, 0.100 mmol), and the mixture was stirred at room temperature for 30 minutes to prepare a 0.0125 mmol / mL toluene solution of (B-482)NiMePy.

[0163] (ii) Homopolymerization of propylene Polymerization was carried out in the same manner as in Example 1(ii), except that 8.0 mL of the toluene solution of (B-482)NiMePy obtained in (i) above was used instead of the 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2. The results are shown in Table 6.

[0164] (Example 5): (X-146) Homopolymerization of propylene using NiMePy (i) Synthesis of metal complexes (X-146)NiMePy was synthesized according to the following scheme.

[0165] [ka]

[0166] All operations were carried out under a nitrogen atmosphere. Dehydrated solvents were used. Nickel chloride hexahydrate (0.51 g, 2.1 mmol) was placed in a 100 mL two-necked eggplant flask, and pyridine (2.0 mL, 25.8 mmol) was added at room temperature. The mixture was stirred at 40 °C for 30 minutes. The reaction mixture instantly changed color from green to turquoise. The volatile components of the reaction mixture were then removed under reduced pressure to obtain NiCl2Py4. A toluene / THF solution (9 / 1 vol%, 20 mL) and pyridine (1.0 mL, 12.9 mmol) were added to the mixture, and the mixture was stirred at 0 °C for 15 minutes to prepare a slurry solution. A solution of methyllithium in diethyl ether (1.09 mol / L, 3.9 mL, 4.3 mmol) was slowly added to the mixture. The solution changed color from yellowish brown to reddish brown. Then, a toluene solution (20 mL) of X-146 (944.1 mg, 1.47 mmol) was quickly added dropwise via cannula at 0°C, and the mixture was heated to 40°C and stirred for 1 hour. The reaction solution remained reddish-brown, but the color slightly lightened. The reaction solution was then filtered through Celite, and the filtrate was concentrated. Hexane (10 mL) was added, and the mixture was cooled to 0°C. The precipitated solid was collected. The resulting solid was then redissolved in toluene (30 mL), the insoluble matter was filtered, and the filtrate was concentrated to obtain (X-146)NiMePy (0.435 g, 35% yield). The obtained (X-146)NiMePy 1 HNMR and 31 The results of PNMR measurement are shown below. 1 HNMR(C6D6,23℃,δ):-1.11(d,J=4.30Hz,3H),0.99(d,J=7.00Hz,6H),1.20(d,J =7.00Hz,6H),2.51-2.61(m,2H),3.67(s,1H),3.72(s,1H),5.03(d,J=6.86Hz,1 H),5.07(d,J=6.86Hz,1H),5.18(s,1H),5.21(s,1H),6.04(t,J=7.44Hz,1H),6. 19(t,J=7.35Hz,1H),6.86(d,J=6.69Hz,1H),7.04-7.35(m,22H),7.64(br,2H). 31 PNMR(C6D6,23℃,δ):43.6(s,1P).

[0167] A complex solution was prepared in the same manner as in Example 4(i), except that the obtained (X-146)NiMePy (83.7 mg, 0.100 mmol) was used.

[0168] (ii) Homopolymerization of propylene Polymerization was carried out in the same manner as in Example 1(ii), except that 8.0 mL of the toluene solution of (X-146)NiMePy obtained in (i) above was used instead of the 0.02 mmol / mL solution of the reaction product of B-482 and Ni(COD)2. The results are shown in Table 6.

[0169] [Table 5]

[0170] [Table 6]

[0171] 4. Discussion As can be seen from Comparative Example 1 in Table 5 above, in polypropylene polymerization using the conventional complex (Comparative Example 1), the molecular weight Mw of the obtained polymer was as small as 2,000. In contrast, as can be seen from Examples 1 and 2 in Table 5 above, in polypropylene polymerization using the metal complexes of the present invention (Examples 1 and 2), the polymerization activity was 1.4 × 10 5 (g / mol / hr) or more, and the molecular weight Mw of the resulting polymer is large, at 10,000 or more. Furthermore, as can be seen from Example 3, when the metal complex of the present invention is used, copolymerization using ethyl 10-undecenoate as a comonomer as a (meth)acrylic acid ester monomer also yielded a copolymerization yield of 7.1 × 10 5 The polymerization activity is also high, and the molecular weight Mw of the resulting copolymer is 10,000 or more, which is as large as that of propylene homopolymerization. Furthermore, from Table 6 above, even in Examples 4 and 5, in which the metal complexes of the present invention were used with different types of transition metal compounds, the molecular weights Mw of the obtained polymers were as large as 10,000 or more. Thus, E that can react with transition metals 1 X having two condensed polycyclic hydrocarbon groups thereon and capable of reacting with a transition metal 1 Ortho position (R 1 The metal complex of the present invention using a ligand having a specific substituent on E 1 It was shown that polypropylene with a significantly higher molecular weight could be obtained compared to the case where a ligand having only one fused polycyclic hydrocarbon group thereon was used (Comparative Example 1). From the above, it is clear that the metal complex of the present invention is of great technical significance since it allows the production of higher molecular weight olefin homopolymers with higher activity than conventional methods.

Claims

1. A method for producing a metal complex, comprising contacting a compound represented by the following general formula [I] or [II] with a transition metal compound containing a nickel atom or a palladium atom: 【Chemistry 1】 [R in formula [I] and [II] １ ~R ６ , E １ , and X １ is as follows: R １ represents an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms. R ２ and R ４ represents a hydrogen atom. R 3 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of a hydrogen atom, a heteroatom, and a group containing a heteroatom. R ５ or R ６ each independently represents a fluorenyl group or a 9,10-dihydroanthracenyl group, which may have a substituent. E １ represents a phosphorus atom. X １ represents an oxygen atom. In addition, in the general formula [I], Z represents a hydrogen atom or a leaving group; m represents the valence of Z.]

2. A metal complex represented by the following general formula [III]: 【Chemistry 2】 [In general formula [III], R １ represents an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms. R ２ and R ４ represents a hydrogen atom. R 3 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of a hydrogen atom, a heteroatom, and a group containing a heteroatom. R ５ or R ６ each independently represents a fluorenyl group or a 9,10-dihydroanthracenyl group, which may have a substituent. E １ represents a phosphorus atom. X １ represents an oxygen atom. M represents a nickel atom or a palladium atom. R ７ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a ligand coordinated to M. L １ represents a ligand coordinated to M. R ７ and L １ may be bonded to each other to form a ring.

3. R １ The method for producing a metal complex according to claim 1, wherein is a substituent represented by the following general formula (1): 【Transformation 3】 (In the general formula (1), R ａ each independently represents a linear or branched acyclic alkyl group having two or more carbon atoms; R ｂ each independently represents a hydrogen atom or a linear or branched acyclic alkyl group, and * represents a bond.

4. The metal complex according to claim 2, wherein R 1 is a substituent represented by the following general formula (1): 【Chemistry 4】 (In the general formula (1), each R a independently represents a linear or branched acyclic alkyl group having two or more carbon atoms, each R b independently represents a hydrogen atom or a linear or branched acyclic alkyl group, and * represents a bond.)

5. R １ The method for producing a metal complex according to claim 1 or 3, wherein is a 2,6-diisopropylphenyl group.

6. The metal complex according to claim 2, wherein R 1 is a 2,6-diisopropylphenyl group.

7. A catalyst component for olefin polymerization, comprising the metal complex according to claim 2, 4, or 6.

8. A method for producing an olefin polymerization catalyst, comprising contacting a compound represented by the following general formula [I] or [II] with a transition metal compound containing a nickel atom or a palladium atom: 【Transformation 5】 [R in formula [I] and [II] １ ~R ６ , E １ , and X １ is as follows: R １ represents an aryl group having 6 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms. R ２ and R ４ represents a hydrogen atom. R 3 represents a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, which may have a group selected from the group consisting of a hydrogen atom, a heteroatom, and a group containing a heteroatom. R ５ or R ６ each independently represents a fluorenyl group or a 9,10-dihydroanthracenyl group, which may have a substituent. E １ represents a phosphorus atom. X １ represents an oxygen atom. In addition, in the general formula [I], Z represents a hydrogen atom or a leaving group; m represents the valence of Z.]

9. R １ The method for producing an olefin polymerization catalyst according to claim 8, wherein: is a substituent represented by the following general formula (1): 【Transformation 6】 (In the general formula (1), R ａ each independently represents a linear or branched acyclic alkyl group having two or more carbon atoms; R ｂ each independently represents a hydrogen atom or a linear or branched acyclic alkyl group, and * represents a bond.

10. R １ The method for producing an olefin polymerization catalyst according to claim 8 or 9, wherein is a 2,6-diisopropylphenyl group.

11. The method for producing an olefin polymerization catalyst according to claim 8, further comprising contacting the catalyst with the following component (B): Component (B): an organoaluminum compound.

12. An olefin polymerization catalyst comprising the olefin polymerization catalyst component according to claim 7.

13. The olefin polymerization catalyst according to claim 12, further comprising the following component (B): Component (B): an organoaluminum compound.

14. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 12 or 13, or the olefin polymerization catalyst obtained by the production method according to any one of claims 8 to 11.

15. The method for producing an olefin polymer according to claim 14, wherein the olefin is propylene.

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