Catalyst for olefin polymerization and method for producing olefin polymer

Abstract

To provide an olefin polymerization catalyst or the like, employing a Group 13 element-containing compound that is useful as a co-catalyst in the olefin polymerization catalyst, capable of effectively activating a transition metal complex as the main catalyst.SOLUTION: The present invention provides a Group 13 element-containing compound (A), represented by the general formula (A), and a transition metal complex (B). Formula (A): [α]γ+{β}γ- [where γ is an integer of 1-5. [α]γ+ is a cation represented by formula [(R1)3 NH]+, [(R2)3C]+ or [(R3)3 N-R4-N(R3)3]γ+ (where a plurality of R1-R4 are C1-30 hydrocarbon groups or the like). {β}γ- is one or more anions, at least one of the anions is an anion represented by formula [MQ4]- (where M is an atom of a Group 13 element, four Q's are independently an aryl group, at least one of four Q's has one or more halogen atoms, selected from chlorine, bromine, and iodine, as substituents].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an olefin polymerization catalyst using a Group 13 element-containing compound useful as a cocatalyst in an olefin polymerization catalyst, and to a method for producing an olefin polymer using the olefin polymerization catalyst. [Background technology]

[0002] In olefin polymerization, borate compounds are widely used as co-catalysts to activate the transition metal complexes that serve as the main catalysts. These borate compounds are ionic compounds consisting of cation-anion ion pairs, and the Lewis acid sites or Bronsted acid sites of the cations contribute to the activation of the transition metal complexes.

[0003] As the cation, tertiary ammonium ions having one hydrogen atom on the nitrogen atom and three substituents selected from alkyl (aliphatic) groups and aryl (aromatic) groups, tertiary carbonium cations having three substituents selected from alkyl groups and aryl groups on the carbon atoms, and polyvalent cations containing these cations are widely used. For example, many technologies have been reported, such as borate compounds of tertiary ammonium ions having aryl groups as substituents on the nitrogen atoms because of their excellent olefin polymerization activity, borate compounds of tertiary trialkylammonium ions having no aryl groups as substituents on the nitrogen atoms because of their excellent affinity with aliphatic hydrocarbon solvents, and borate compounds of polyvalent cations having multiple tertiary ammonium ions in which multiple nitrogen atoms are bridged by hydrocarbon groups (e.g., Patent Documents 1 to 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 1991 / 009882 [Patent Document 2] International Publication No. 2019 / 210026 [Patent Document 3] International Publication No. 2019 / 210030 [Patent Document 4] International Publication No. 1997 / 035893 [Patent Document 5] Japanese Patent Publication No. 2022-069397 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional borate compounds have room for further improvement in terms of olefin polymerization activity. In view of the above-mentioned conventional techniques, the present invention aims to provide an olefin polymerization catalyst using a Group 13 element-containing compound, which is useful as a co-catalyst in an olefin polymerization catalyst and has excellent activating performance for a transition metal complex, which is the main catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Means for solving the problem]

[0006] The present invention relates to, for example, the following [1] to [6]. [1] An olefin polymerization catalyst comprising a Group 13 element-containing compound (A) represented by the following general formula (A) and a transition metal complex (B): [α] γ+ {β} γ- …(A) [In the general formula (A), γ is an integer of 1 to 5. [α] γ+ is a cation represented by the following general formula (α-1), (α-2) or (α-3). [(R 1 )3NH] + …(α-1) [(R 2 )3C] + …(α-2) [(R 3 )3N-R 4 -N(R 3 )3] γ+ …(α-3) (In the general formulae (α-1), (α-2) and (α-3), a plurality of R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a hydrocarbon group having 1 to 30 carbon atoms, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms, and may be bonded to each other to form a ring. 4 is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group containing a hetero atom, and R 4 and one or more R 3 may be bonded to each other to form a ring. {β} γ- represents one or more anions (β), and the total valence of the anions (β) is γ. The anions (β) are anions (β-1) represented by the following general formula (β-1) or anions (β-2) other than the anions (β-1): [MQ4] - …(β-1) (In the general formula (β-1), M is an atom of a Group 13 element. The four Qs are independently aryl groups, and at least one of the four Qs is an aryl group (Q-0) having one or more halogen atoms selected from a chlorine atom, a bromine atom, and an iodine atom as a substituent. At least one of the anions (β) is the anion (β-1). When a plurality of anions (β) are present, they may be the same or different.

[0007] [2] The olefin polymerization catalyst according to [1], wherein in the general formula (A), at least one of the aryl groups (Q-0) is an aryl group represented by the following general formula (Q-1):

[0008] [ka] In the general formula (Q-1), * represents a bond to the M, and a plurality of X a are independently halogen atoms selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and a plurality of X a At least one of the groups is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0009] [3] In the general formula (Q-1), two X's located at meta positions with respect to the bond to M a at least one of which is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0010] [4] The olefin polymerization catalyst according to [3], wherein the aryl group represented by the general formula (Q-1) is an aryl group represented by the following general formula (Q-1a) or (Q-1b):

[0011] [ka] In general formulae (Q-1a) and (Q-1b), * represents a bond to the M, and a plurality of X m are independently a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0012] [5] The olefin polymerization catalyst according to any one of [1] to [4], wherein in the general formula (A), M is a boron atom.

[0013] [6] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [1] to [5]. [Effects of the Invention]

[0014] According to the present invention, there are provided an olefin polymerization catalyst using a Group 13 element-containing compound, which is useful as a co-catalyst in an olefin polymerization catalyst and has excellent activating performance for a transition metal complex, which is the main catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be described in further detail. [Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention contains a Group 13 element-containing compound (A) and a transition metal complex (B).

[0016] <Compounds containing Group 13 elements (A)> The Group 13 element-containing compound (A) (hereinafter also simply referred to as "compound (A)") used in the olefin polymerization catalyst of the present invention is characterized by being represented by the following general formula (A). [α] γ+ {β} γ- …(A) [In general formula (A), [α] γ+ is a given cation. {β} γ- is a predetermined anion.

[0017] <γ> In the general formula (A), γ is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0018] <[α] γ+ > In general formula (A), [α] γ+ is a cation represented by the following general formula (α-1), (α-2) or (α-3). [(R 1 )3NH] + …(α-1) [(R 2 )3C] + …(α-2) [(R 3 )3N-R4 -N(R 3 )3] γ+ …(α-3)

[0019] 《R 1 , R 2 , R 3 》 In the general formulae (α-1), (α-2) and (α-3), a plurality of R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a hydrocarbon group having 1 to 30 carbon atoms, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or heteroatom-containing hydrocarbon group have been substituted with silicon atoms or germanium atoms. 1 Comrade, R 2 R 3 may be the same or different and may be bonded to each other to form a ring.

[0020] (halogen atom) Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0021] (hydrocarbon group) Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. An alicyclic hydrocarbon group may contain an aliphatic hydrocarbon moiety, and an aromatic hydrocarbon group may contain an aliphatic hydrocarbon moiety and / or an alicyclic hydrocarbon moiety.

[0022] The hydrocarbon group may or may not have an unsaturated bond, and the aliphatic hydrocarbon group may be linear or branched. Specific examples of the hydrocarbon group include: Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, n-icosyl, isopropyl, sec-butyl, tert-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl (1,1-dimethylpropyl), cyamyl, pentan-3-yl, 2-methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl (2-methylpentan-2-yl), 3-methylpentan-2-yl linear or branched alkyl groups having 1 to 30 carbon atoms, such as a 4-methylpentan-2-yl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a thexyl group, a 3-methylpentan-3-yl group, a 3,3-dimethylbut-2-yl group, a hexane-3-yl group, a 2-methylpentan-3-yl group, a heptan-4-yl group, a 2,4-dimethylpentan-2-yl group, a 3-ethylpentan-3-yl group, a 4,4-dimethylpentyl group, a 4-methylheptan-4-yl group, a 4-propylheptan-4-yl group, a 2,3,3-trimethylbutan-2-yl group, or a 2,4,4-trimethylpentan-2-yl (tert-octyl group); Vinyl group, allyl group, propenyl group, isopropenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, isopentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1- yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en- 1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethyl-pent-1-en-3 linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 30 carbon atoms, such as a 2-(cyclopentadienyl)-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group; Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 30 carbon atoms, such as pent-1-yn-yl, pent-4-yn-2-yl, hex-1-yn-1-yl, 3,3-dimethyl-but-1-yn-1-yl, 2-methyl-pent-3-yn-2-yl, 2,2-dimethyl-but-3-yn-1-yl, hex-4-yn-1-yl, and hex-5-yn-1-yl; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1, 6-dien-4-yl group, 1,2,3-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-isopropylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,(5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl ) Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 30 carbon atoms, such as diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, and 2-(1-azulenyl)ethyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohex Sil group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl- tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1 cyclic saturated and unsaturated hydrocarbon groups having 3 to 30 carbon atoms, such as -(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl, indenyl, fluorenyl, indacenyl, tetrahydroindacenyl, benzoindenyl, and azulenyl; Phenyl group, tolyl group (o-tolyl group, m-tolyl group, p-tolyl group), 4-n-butylphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group, 4-n-octadecylphenyl group, 4-iso-propylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-iso-butylphenyl group, 4-iso- Pentylphenyl group, 4-neopentylphenyl group, 4-tert-pentylphenyl group, 4-(pentan-3-yl)phenyl group, 4-iso-hexylphenyl group, 4-(1,1-dimethylbutyl)phenyl group, 4-(3,3-dimethylbutyl)phenyl group, 4-thexylphenyl group, 4-(3-methylpentan-3-yl)phenyl group, 4-(heptan-4-yl)phenyl group, 4-(2,4-dimethylpentan-2-yl)phenyl group, 4-(3-ethylpentan-3-yl)phenyl group, 4-(4,4-dimethylpentyl)phenyl group nyl group, 4-(4-methylheptan-4-yl)phenyl group, 4-(4-propylheptan-4-yl)phenyl group, 4-(2,4,4-trimethylpentan-2-yl)phenyl group, 4-adamantylphenyl group, 3-n-butylphenyl group, 3-n-pentylphenyl group, 3-n-hexylphenyl group, 3-n-heptylphenyl group, 3-n-octylphenyl group, 3-n-nonylphenyl group, 3-n-decylphenyl group, 3-n-undecylphenyl group, 3-n-dodecylphenyl group, 3-n-octadecylphenyl group, 3-is o-Propylphenyl group, 3-sec-butylphenyl group, 3-tert-butylphenyl group, 3-iso-butylphenyl group, 3-iso-pentylphenyl group, 3-neopentylphenyl group, 3-tert-pentylphenyl group, 3-(pentan-3-yl)phenyl group, 3-iso-hexylphenyl group, 3-(1,1-dimethylbutyl)phenyl group, 3-(3,3-dimethylbutyl)phenyl group, 3-thexylphenyl group, 3-(3-methylpentan-3-yl)phenyl group, 3-(heptan-4-yl)phenyl group, 3-(2,4-dimethylpentan-2-yl)phenyl group, 3-(3-ethylpentan-3-yl)phenyl group, 3-(4,4-dimethylpentyl)phenyl group, 3-(4-methylheptan-4-yl)phenyl group, 3-(4-propylheptan-4-yl)phenyl group, 3-(2,4,4-trimethylpentan-2-yl)phenyl group, 3-adamantylphenyl group, 2-n-butylphenyl group, 2-n-pentylphenyl group, 2-n-hexylphenyl group, 2-n-heptylphenyl group, 2-n-octylphenyl group, 2-n-nonylphenyl group, 2-n-decylphenyl group, 2-n-undecylphenyl group, 2-n-dodecylphenyl group, 2-n-octadecylphenyl group, 2-iso-propylphenyl group, 2-sec-butylphenyl group, 2-tert-butylphenyl group, 2-iso-butylphenyl group, 2-iso-pentylphenyl group, 2-neopentylphenyl group, 2-tert-pentylphenyl group, 2-(pentan-3-yl)phenyl group, 2-iso-hexylphenyl group, 2-(1,1-dimethylbutyl)phenyl group, 2-(3,3-dimethylbutyl)phenyl group nyl group, 2-thexylphenyl group, 2-(3-methylpentan-3-yl)phenyl group, 2-(heptan-4-yl)phenyl group, 2-(2,4-dimethylpentan-2-yl)phenyl group, 2-(3-ethylpentan-3-yl)phenyl group, 2-(4,4-dimethylpentyl)phenyl group, 2-(4-methylheptan-4-yl)phenyl group, 2-(4-propylheptan-4-yl)phenyl group, 2-(2,4,4-trimethylpentan-2-yl)phenyl group, 2-adamantylphenyl group, xylyl group (2,3-dimethylphenyl) n-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl), 3,5-di-tert-butylphenyl, 3,5-di-n-octylphenyl, 3,5-di-n-dodecylphenyl, 3,5-di-n-octadecylphenyl, 3,5-di(2,4,4-trimethylpentan-2-yl)phenyl, 3,5-diadamantylphenyl, mesityl, cumenyl, duralyl, 2,6-di-isopropylphenyl, 2,4,Examples of aromatic substituents having 6 to 30 carbon atoms include a 6-tri-isopropylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

[0023] Among the linear or branched alkyl groups having 1 to 30 carbon atoms, 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, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-octadecyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a pentan-3-yl group, an isohexyl group, a 1,1-dimethylbutyl group, a 3,3-dimethylbutyl group, a thexyl group, a 3-methylpentan-3-yl group, a heptane-4-yl group, a methyl group, an ethyl group, an n-propyl group, an ethyl group, an n-pentyl group, an ethyl ... Preferred are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-dodecyl, n-octadecyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, 2,4,4-trimethylpentan-2-yl, and the like, and more preferred are hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-dodecyl, n-octadecyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, 2,4,4-trimethylpentan-2-yl, and tert-octyl. When the number of carbon atoms in the hydrocarbon group is reduced, compound (A) tends to have a lower affinity with the hydrocarbon medium when used as a catalyst component in the hydrocarbon medium, which improves catalyst immobilization and activation performance.

[0024] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 30 carbon atoms, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group, a methallyl group, a pent-4-en-1-yl group, a prenyl group, a penta-1,4-dien-3-yl group, a hex-5-en-1-yl group, a 2-methylpent-4-en-2-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, and the like are preferred, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, and a hex-5-en-1-yl group are more preferred.

[0025] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 30 carbon atoms, an ethynyl group, a propargyl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a penta-3-yn-1-yl group, a penta-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a hex-4-yn-1-yl group, a hex-5-yn-1-yl group, and the like are preferred, and a propa-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, and a but-3-yn-1-yl group are more preferred.

[0026] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 30 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-isopropylphenyl)ethyl group, 2-(4-t Preferred are a 2-(3,5-di-tert-butylphenyl)ethyl group, a 2-(3,5-di-tert-butylphenyl)ethyl group, a styryl group, a 2-methyl-1-phenylpropan-2-yl group, a 3-phenylpropyl group, a cinnamyl group, a neophyl group, a cyclopentadienyldiphenylmethyl group, a 2-(1-indenyl)propan-2-yl group, a (1-indenyl)diphenylmethyl group, a 2-(1-indenyl)ethyl group, a 2-(9-fluorenyl)propan-2-yl group, a (9-fluorenyl)diphenylmethyl group, and a 2-(9-fluorenyl)ethyl group, and more preferred are a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a cinnamyl group.

[0027] Among the above-mentioned saturated and unsaturated cyclic hydrocarbon groups having 3 to 30 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, a 1-allylcyclopentyl group, a 1-benzylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, a 1-allylcyclohexyl group, a 1-benzylcyclohexyl group, a cycloheptyl group, a cycloheptenyl group, a cycloheptatrienyl group, a 1-methylcycloheptyl group, a 1-allylcycloheptyl group, a 1-benzylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a cycloheptyl group, a cycloheptatrienyl group, a 1-methylcycloheptyl group, a 1-allylcycloheptyl group, a cyclohex ... Preferred are cycloheptyl, cyclooctyl, cyclooctenyl, cyclooctadienyl, 4-cyclohexyl-tert-butyl, norbornyl, 2-methylbicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.2]octan-1-yl, 1-adamantyl, 2-adamantyl, pentalenyl, indenyl, and fluorenyl groups, and more preferred are cyclopentyl, cyclopentenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexenyl, 1-methylcyclohexyl, and 1-adamantyl groups.

[0028] Among the aromatic substituents having 6 to 30 carbon atoms, a phenyl group, a tolyl group, a 4-n-hexylphenyl group, a 4-n-heptylphenyl group, a 4-n-octylphenyl group, a 4-n-decylphenyl group, a 4-n-dodecylphenyl group, a 4-n-octadecylphenyl group, a 4-tert-butylphenyl group, a 4-(2,4,4-trimethylpentan-2-yl)phenyl group, a 4-adamantylphenyl group, a 3-n-hexylphenyl group, a 3-n-hept ... Phenyl group, 3-n-octylphenyl group, 3-n-decylphenyl group, 3-n-dodecylphenyl group, 3-n-octadecylphenyl group, 3-tert-butylphenyl group, 3-(2,4,4-trimethylpentan-2-yl)phenyl group, 3-adamantylphenyl group, xylyl group, 3,5-di-tert-butylphenyl group, 3,5-di-n-octylphenyl group, 3,5-di-n-dodecylphenyl group, 3,5-di-n-octadecylphenyl group Preferred are an aryl group, a 3,5-di(2,4,4-trimethylpentan-2-yl)phenyl group, a 3,5-diadamantylphenyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, an allylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, and a ferrocenyl group. More preferred are a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a 4-(2,4,4-trimethylpentan-2-yl)phenyl group, an allylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group.

[0029] (heteroatom-containing hydrocarbon group) One example of the heteroatom-containing hydrocarbon group is one in which some or all of the hydrogen atoms in the hydrocarbon group have been replaced with halogen atoms or a heteroatom-containing group. Examples of the heteroatom-containing group include an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, and a phosphorus-containing group.

[0030] Examples of the groups substituted with halogen atoms include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a pentafluoroethyl group, a pentachloroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a nonachlorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, iodophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group, bis(trimethylsilyl)trifluorophenyl group, bis(triisopropylsilyl)trifluorophenyl group, bis(tert-butyldimethylsilyl)trifluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, bis(trifluoromethyl)fluorophenyl group, bis(trifluoromethyl)trifluorophenyl group, pentafluorobenzyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluoro Examples of such groups include a difluorobiphenyl group, a trifluorobiphenyl group, a tetrafluorobiphenyl group, a pentafluorobiphenyl group, a perfluorobiphenyl-2-yl group, a perfluorobiphenyl-3-yl group, a di-tert-butyl-fluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxybiphenyl group, a bistrifluoromethoxybiphenyl group, a trifluoromethyldimethylsilyl group, a trifluoromethoxy group, a pentafluoroethoxy group, a fluorophenoxy group, a difluorophenoxy group, a trifluorophenoxy group, a pentafluorophenoxy group, a di-tert-butyl-fluorophenoxy group, a trifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a trifluoromethoxyphenoxy group, a bistrifluoromethoxyphenoxy group, a difluoromethylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, a trifluoromethylthio group, an α-perfluoronaphthyl group, and a β-perfluoronaphthyl group.

[0031] Among those substituted with halogen atoms, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, and a trifluoromethylthio group are preferred, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group are more preferred.

[0032] Examples of the oxygen-containing group include a hydroxymethyl group, a hydroxyethyl group, a 2-hydroxydodecyl group, a 2-hydroxyoctadecyl group, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyloxy group, an octyloxy group, a tert-octyloxy group, a decyloxy group, a dodecyloxy group, an octa ... Decyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, isopropylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, isopropoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxy Examples of such groups include a diethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group.

[0033] Among the oxygen-containing groups, a hydroxymethyl group, a hydroxyethyl group, a 2-hydroxydodecyl group, a 2-hydroxyoctadecyl group, a methoxy group, an ethoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a tert-butoxy group, a prenyloxy group, an octyloxy group, a tert-octyloxy group, a decyloxy group, a dodecyloxy group, an octadecyloxy group, a benzyloxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an isopropylphenoxy group, a oxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-(2-ethoxyethoxy)ethoxy group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, A xolanyl group, a dioxanyl group, a dimethyldioxanyl group, a methoxyphenyl group, an isopropoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, a dibenzofuryl group, and the like are preferred, and a hydroxyethyl group, a 2-hydroxydodecanyl group, and the like are also preferred. A sil group, a 2-hydroxyoctadecyl group, a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxymethyl group, a dioxolanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a benzofuryl group, and a dibenzofuryl group are more preferred.

[0034] Examples of the nitrogen-containing group include a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, an N,N-dihexylamino group, an N,N-didecylamino group, an N,N-didodecylamino group, an N,N-dioctadecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3, Examples of such groups include a 5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-isopropyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolylphenyl group, a pyridylphenyl group, a quinolylphenyl group, an isoquinolylphenyl group, an indolinylphenyl group, an indolylphenyl group, a carbazolylphenyl group, a di-tert-butylcarbazolylphenyl group, a pyrrolyl group, a methylpyrrolyl group, a phenylpyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

[0035] Among the nitrogen-containing groups, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a dimethylaminomethyl group, a benzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolylphenyl group, a carbazolylphenyl group, a di-tert-butylcarbazolyl group, A phenyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, a benzoxazolyl group, and the like are preferred, and an amino group, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-isopropyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group are more preferred.

[0036] Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenylthio Examples of such groups include a thioallyl group, a naphthylthioallyl group, a mercaptophenyl group, a methylthiophenyl group, a thienylphenyl group, a methylthienylphenyl group, a benzothienylphenyl group, a dibenzothienylphenyl group, a benzodithienylphenyl group, a thienyl group, a tetrahydrothienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, and a thiazolidinyl group.

[0037] Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group, and a benzothiazolyl group are preferred.

[0038] Examples of the phosphorus-containing group include a dimethylphosphino group, a diethylphosphino group, a di-n-propylphosphino group, a diisopropylphosphino group, a dicyclopentylphosphino group, a dicyclohexylphosphino group, a di(methylcyclohexyl)phosphino group, a di-n-butylphosphino group, a di-sec-butylphosphino group, a di-tert-butylphosphino group, an ethyldecylphosphino group, a diundecylphosphino group, a didodecylphosphino group, a methyldodecylphosphino group, a dioctadecylphosphino group, a diphenylphosphino group, a di(o-tolyl)phosphino group, a di(m-tolyl)phosphino group, a di(p-tolyl)phosphino group, a di(pentafluorophenyl)phosphino group, and a di(trifluoromethyl)phosphino group.

[0039] Among the phosphorus-containing groups, a dioctadecylphosphino group and a di(pentafluorophenyl)phosphino group are preferred.

[0040] Other examples of the heteroatom-containing hydrocarbon group include groups in which some of the methylene groups in the hydrocarbon group have been replaced with a structure represented by -CO-, -CH(OH)-, -NR-, -PR-, -P(O)(R)- (where R is a hydrogen atom or a hydrocarbon group (having, for example, 1 to 10 carbon atoms)), -O-, -S-, or -SO2-, and groups in which some of the methine groups in the hydrocarbon group have been replaced with a nitrogen atom, a phosphorus atom, or a structure represented by ≡SiH (wherein the number of carbon atoms in the cations represented by general formulae (α-1), (α-2), and (α-3) is selected within a range such that the number of carbon atoms is 30 or less).

[0041] Other examples of the heteroatom-containing hydrocarbon group include residues obtained by removing two hydrogen atoms from a polymer having a heteroatom, and examples of such polymers include polyaniline, polypyrrole, polyacrylonitrile, polyethyleneimine, and polyamide. A proton may be coordinately bonded to some or all of the heteroatoms (preferably nitrogen atoms) contained in the heteroatom-containing hydrocarbon group.

[0042] (Groups in which some or all of the carbon atoms of the hydrocarbon groups and heteroatom-containing hydrocarbon groups have been replaced with silicon atoms and germanium atoms) Examples of the substituent include a silyl group, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenyldiphenylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluoren ... Examples thereof include an olefinyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, a trimethylgermyl group, a triethylgermyl group, a tert-butyldimethylgermyl group, a 4-trimethylgermylphenyl group, a 4-triethylgermylphenyl group, a 4-tri-isopropylgermylphenyl group, and a 3,5-bis(trimethylgermyl)phenyl group.

[0043] Among the above substituents, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, and a trifluorosilyl group are more preferred.

[0044] 《R 4 》 In general formula (α-3), R 4 R is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group containing a hetero atom. 4 and one or more R 3 may be bonded to each other to form a ring.

[0045] (hydrocarbon group) Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. An alicyclic hydrocarbon group may contain an aliphatic hydrocarbon moiety, and an aromatic hydrocarbon group may contain an aliphatic hydrocarbon moiety and / or an alicyclic hydrocarbon moiety.

[0046] The hydrocarbon group may or may not have an unsaturated bond, and the aliphatic hydrocarbon group may be linear or branched. Examples of saturated aliphatic hydrocarbon groups include a methylene group; and alkylene groups such as an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 2-methylpropylene group, a pentamethylene group, a 2-methylbutylene group, a 2-ethylpropylene group, a hexamethylene group, a 2-ethylbutylene group, a heptamethylene group, a 2-ethylpentylene group, a 2-methylhexylene group, an octamethylene group, a 2-ethylhexylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tetradecamethylene group, a hexadecamethylene group, an octadecamethylene group, a 2-ethyloctadecene group, and an icosene group.

[0047] The alkylene group has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and even more preferably 2 to 6 carbon atoms.

[0048] Examples of unsaturated aliphatic hydrocarbon groups include those in which some or all of the carbon-carbon single bonds in the above-mentioned alkylene groups have been replaced with double bonds, such as groups represented by -CH=CH-, -CH2CH=CH-, -CH2CH2CH=CH-, -CH2CH=CHCH2-, -CH2C(CH3)=CH-, -CH2-C(=CH2)-CH2-, -CH(CH2CH3)-CH2CH2CH=CH-, -CH2CH2CH=CH-CH=CH-, and -CH2CH=CH-CH(CH3)-CH=CH-CH2-.

[0049] The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a cyclopropylene group, a cyclobutane-1,2-diyl group, a cyclobutane-1,3-diyl group, a cyclopentane-1,2-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, a cyclohexane-1,4-diyl group, a 3-cyclohexene-1,2-diyl group, a 2,5-cyclohexadiene-1,4-diyl group, a cycloheptane-1,4-diyl group, a cyclooctane-1,4-diyl group, a spiro[3,4]octane-2,7-diyl group, and a spiro[4,5]deca-1,6-diene-3,9-diyl group. Further examples of groups having an aliphatic hydrocarbon moiety include groups represented by the following formula:

[0050] [ka]

[0051] The alicyclic hydrocarbon group has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 3 to 6 carbon atoms.

[0052] The aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include an o-phenylene group, a p-phenylene group, an m-phenylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a biphenyl-4,4′-diyl group, a 1,5-anthrylene group, a 2,6-anthrylene group, an o-terphenyl-4,4″-diyl group, a p-terphenyl-4,4″-diyl group, an m-terphenyl-4,4″-diyl group, a 2,7-phenanthrylene group, and a 1,6-pyrenylene group. Further examples of groups having an aliphatic hydrocarbon moiety include groups represented by the following formula:

[0053] [ka]

[0054] The aromatic hydrocarbon group has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 carbon atoms.

[0055] (heteroatom-containing hydrocarbon group) One example of the heteroatom-containing hydrocarbon group is one in which some or all of the hydrogen atoms in the hydrocarbon group have been replaced with halogen atoms or a heteroatom-containing group. Examples of the heteroatom-containing group include a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, and a sulfur-containing group, and the nitrogen-containing group is preferred.

[0056] The halogen atom or heteroatom-containing group may be substituted with the above-mentioned R 1 ~R 3 Specific examples of the heteroatom-containing hydrocarbon group in the above formula (1) are the same as those in the above formula (1).

[0057] Other examples of the heteroatom-containing hydrocarbon group include groups in which some of the methylene groups in the hydrocarbon group have been replaced with a structure represented by -CO-, -CH(OH)-, -NR-, -PR-, -P(O)(R)- (where R is a hydrogen atom or a hydrocarbon group (having, for example, 1 to 10 carbon atoms)), -O-, -S-, or -SO2-, and groups in which some of the methine groups in the hydrocarbon group have been replaced with a nitrogen atom, a phosphorus atom, or a structure represented by ≡SiH (wherein the number of carbon atoms in the cation represented by general formula (α-3) is selected within a range such that the number of carbon atoms is 30 or less).

[0058] Some or all of the heteroatoms (preferably nitrogen atoms) contained in the heteroatom-containing hydrocarbon group may have an [α] γ+ The proton may be coordinately bonded within the range in which the valence γ falls within the above range.

[0059] 《[α] γ+ Examples of [α] γ+ Specific examples of the cation include those represented by the following formula:

[0060] [ka]

[0061] <{β} γ- > In the general formula (A), {β} γ- is the above [α] γ+ represents the anion pair of {β} γ- represents one or more anions (β), and the total valence of the anions (β) is γ. The anions (β) are anions (β-1) represented by the following general formula (β-1) or anions (β-2) other than the anions (β-1): [MQ4] - …(β-1) At least one of the anions (β) is the anion (β-1). When a plurality of the anions (β) are present, they may be the same or different.

[0062] [Anion (β-1)] "M" M represents an atom of an element of Group 13. Examples of the atom of an element of Group 13 include a boron atom (B), an aluminum atom (Al), a gallium atom (Ga), an indium atom (In), and a thallium atom (Tl), of which a boron atom and an aluminum atom are preferred, and a boron atom is more preferred.

[0063] Q The four Qs are independently an aryl group, and at least one of the four Qs is an aryl group (Q-0) having one or more halogen atoms selected from a chlorine atom, a bromine atom, and an iodine atom as a substituent. Preferably, all of the four Qs are independently the aryl group (Q-0). From the viewpoint of ease of production or availability, it is more preferable that all of the four Qs are the same aryl group (Q-0).

[0064] (aryl group) Examples of the aryl group include the aromatic hydrocarbon groups having 6 to 30 carbon atoms and the aromatic hydrocarbon groups in which some or all of the hydrogen atoms have been replaced with halogen atoms or heteroatom-containing groups, and are preferably aryl groups having 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0065] Examples of the aryl group (Q-0) having one or more halogen atoms selected from a chlorine atom, a bromine atom, and an iodine atom as substituents include, among the aforementioned "aromatic hydrocarbon group in which some or all of the hydrogen atoms have been replaced with halogen atoms or heteroatom-containing groups," those in which at least one hydrogen atom has been replaced with a halogen atom, and at least one of the replaced halogen atoms is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0066] Specific examples of the aryl group (Q-0) include a chlorophenyl group, a bromophenyl group, an iodophenyl group, a dichlorophenyl group, a dibromophenyl group, a diiodophenyl group, a trichlorophenyl group, a tribromophenyl group, a triiodophenyl group, a tetrachlorophenyl group, a tetrabromophenyl group, a tetraiodophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentaiodophenyl group, a chlorotetrafluorophenyl group, a bromotetrafluorophenyl group, an iodotetrafluorophenyl group, a dichlorotrifluorophenyl group, a dibromotrifluorophenyl group, a diiodotrifluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, an iodonaphthyl group, an α-pa Examples of such groups include a β-chloronaphthyl group, a β-perchloronaphthyl group, a 3,5-bis(chlorotetrafluorophenyl)-2,4,6-trifluorophenyl group, a 3,5-bis(bromotetrafluorophenyl)-2,4,6-trifluorophenyl group, a 3,5-bis(iodotetrafluorophenyl)-2,4,6-trifluorophenyl group, a 3,5-bis(pentachlorophenyl)-2,4,6-trifluorophenyl group, a 4-(chlorotetrafluorophenyl)-2,3,5,6-tetrafluorophenyl group, a 4-(bromotetrafluorophenyl)-2,3,5,6-tetrafluorophenyl group, and a 4-(iodotetrafluorophenyl)-2,3,5,6-tetrafluorophenyl group.

[0067] In compound (A), at least one of the aryl groups (Q-0) is preferably an aryl group (Q-1) represented by the following general formula (Q-1), more preferably each of the aryl groups (Q-0) is independently the aryl group (Q-1), and further preferably each of the aryl groups (Q-0) is the same aryl group (Q-1).

[0068] [ka]

[0069] In the general formula (Q-1), * represents [MQ4] -The bond to atom M of a group 13 element in the molecule is shown. In the general formula (Q-1), a plurality of X a are independently halogen atoms selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and a plurality of X a At least one of X is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom. a At least one of the groups is preferably a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0070] Specific examples of the aryl group (Q-1) include a chlorotetrafluorophenyl group, a bromotetrafluorophenyl group, an iodotetrafluorophenyl group, a dichlorotrifluorophenyl group, a dibromotrifluorophenyl group, a diiodotrifluorophenyl group, a trichlorodifluorophenyl group, a tribromodifluorophenyl group, a triiododifluorophenyl group, a tetrachlorofluorophenyl group, a tetrabromofluorophenyl group, a tetraiodofluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentaiodophenyl group, a chlorobromotrifluorophenyl group, a chloroiodotrifluorophenyl group, a bromoiodotrifluorophenyl group, and a chlorobromoiododifluorophenyl group.

[0071] The aryl group represented by the general formula (Q-1) is preferably an aryl group represented by the following general formula (Q-1a) or (Q-1b).

[0072] [ka]

[0073] In the general formulas (Q-1a) and (Q-1b), * represents [MQ4] - The bond to atom M of a group 13 element in the mare independently a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

[0074] Specific examples of the aryl group represented by general formula (Q-1a) or (Q-1b) include a 3-chlorotetrafluorophenyl group, a 3-bromotetrafluorophenyl group, a 3-iodotetrafluorophenyl group, a 3,5-dichloro-2,4,6-trifluoro group, a 3,5-dibromo-2,4,6-trifluoro group, a 3,5-diiodo-2,4,6-trifluoro group, a 3-chloro-5-bromo-2,4,6-trifluorophenyl group, a 3-chloro-5-iodo-2,4,6-trifluorophenyl group, and a 3-bromo-5-iodo-2,4,6-trifluorophenyl group.

[0075] As the aryl group represented by the general formula (Q-1), in the general formulas (Q-1a) and (Q-1b), X m is a chlorine atom.

[0076] <Example of anion (β-1)> Specific examples of the anion (β-1) include tetrakis(3-chlorotetrafluorophenyl)borate ion, tetrakis(3-bromotetrafluorophenyl)borate ion, tetrakis(3-iodotetrafluorophenyl)borate ion, tetrakis(3,5-dichloro-2,4,6-trifluorophenyl)borate ion, tetrakis(3,5-dibromo-2,4,6-trifluorophenyl)borate ion, tetrakis(3,5-diiodo-2,4,6-trifluorophenyl)borate ion, tris(pentafluorophenyl)(pentachlorophenyl)borate ion, tris(3,5-dichloro-2,4,6-trifluorophenyl)(pentafluorophenyl)borate ion, tris(3,5-dichloro-2,4,6-trifluorophenyl)(α-perfluoronaphthyl)borate ion, bis(3,5-dibromo-2,4,6-trifluorophenyl)bis(pentafluorophenyl)borate ion, tris(pentafluorophenyl)(pentachlorophenyl)borate ion, tris(pentafluorophenyl)(α-perfluoronaphthyl)borate ion, bis(pentafluorophenyl)bis(pentafluorophenyl)borate ion, tris(pentafluorophenyl) ... Tris(3,5-dichloro-2,4,6-trifluorophenyl)(3,5-bis(pentafluorophenyl)borate ion, bis(3,5-dibromo-2,4,6-trifluorophenyl)bis(pentafluorophenyl)borate ion, tris(3,5-dichloro-2,4,6-trifluorophenyl)(4-trimethylsilylphenyl)borate ion, tris(3,5-dichloro-2,4,6-trifluorophenyl)(hydroxyphenyl)borate ion, Examples include tris(3,5-dichloro-2,4,6-trifluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate ion, tris(3,5-dichloro-2,4,6-trifluorophenyl)(6-hydroxy-2-naphthyl)borate ion, tris(3,5-dichloro-2,4,6-trifluoro)(4-hydroxyphenylphenyl)borate ion, and anions in which the boron atom in these anions is replaced with an atom of one of the other Group 13 elements mentioned above. Among these, tetrakis(3,5-dichloro-2,4,6-trifluorophenyl)borate ion is preferred.

[0077] [Anion (β-2) other than anion (β-1)] Examples of the anion (β-2) include anions other than the anion (β-1), namely, a tetrakispentafluorophenylborate ion, a tetrakis(α-perfluoronaphthylborate)borate ion, a tetrakis(β-perfluoronaphthylborate)borate ion, a carboxylate ion, a benzoate ion, an amide, a sulfate ester ion, a sulfonate ion, a hexafluorophosphate ion, a phosphate ester ion, a phosphonate ion, a fluoride ion, a chloride ion, a bromide ion, and an iodide ion, and the tetrakispentafluorophenylborate ion, the hexafluorophosphate ion, and the chloride ion are preferred.

[0078] <Specific Examples of Group 13 Element-Containing Compound (A)> Specific examples of the compound (A) include compounds represented by the following formulas (A-1) to (A-6).

[0079] [ka]

[0080] [ka]

[0081] The compound represented by formula (A-5) has two anions (β) (one anion (β-1) and one anion (β-2) (chloride ion)), and the total valence thereof is 2. The compound represented by formula (A-6) has three anions (β) (one anion (β-1) and two anions (β-2) (tetrakispentafluorophenylborate ion and hexafluorophosphate ion), and the total valence thereof is 3.

[0082] <Method for producing Group 13 element-containing compound (A)> Examples of methods for producing compound (A) include methods using the methods described in U.S. Patent Application Publication No. 2019 / 0330392, U.S. Patent No. 5,493,056, and European Patent No. 0426637. Specifically, compound (A) can be mainly produced by the following method.

[0083] The cation [α] γ+ Compounds containing ([α] γ+ Hydrochloride salts, including [α] γ+ and the anion {β} γ- By mixing the compound (A) with a salt containing the Group 13 element (lithium borate salt, sodium aluminate salt, etc.) in a solvent (cyclohexane, dichloromethane, methylcyclohexane, etc.), the target Group 13 element-containing compound (compound (A)) and the by-product alkali metal chloride can be synthesized, and compound (A) can be isolated by removing the latter by filtration.

[0084] The cation [α] γ+ The compound containing [(R 1 )3NH] + The hydrochloride salt is synthesized by dissolving the amine, which has a structure in which one proton has been removed from , in a solvent (dichloromethane, diethyl ether, hexane, cyclohexane, methylcyclohexane, toluene, etc.) and adding one or more equivalents of hydrogen chloride. The resulting hydrochloride salt is isolated by filtration.

[0085] <Transition Metal Complex (B)> The transition metal complex (B) is not particularly limited, and examples thereof include transition metal complexes used in conventionally known olefin polymerization catalysts.

[0086] Examples of the transition metal complex (B) include at least one metallocene compound selected from the group consisting of a compound represented by the following general formula (B1) (unbridged metallocene compound), a compound represented by the following general formula (B2) (bridged metallocene compound), and a compound represented by the following general formula (B3) (half metallocene compound).

[0087] [ka]

[0088] In the general formulas (B1) to (B3), M represents an atom of Group 4 or 5 of the periodic table. Specific examples of M include a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, and a tantalum atom, and preferably a titanium atom, a zirconium atom, or a hafnium atom.

[0089] In the general formulae (B1) to (B3), Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group (i.e., a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom), a neutral conjugated or non-conjugated diene, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.

[0090] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms; an alicyclic hydrocarbon group having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms; and an aromatic hydrocarbon group having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms.

[0091] Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, 1,1-dimethylbutyl, and 1,1,3-trimethylbutyl; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as vinyl, allyl, and isopropenyl; and linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as ethynyl and propargyl.

[0092] Examples of the alicyclic hydrocarbon group include saturated cyclic hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-methyl-1-cyclohexyl group, and an adamantyl group; and unsaturated cyclic hydrocarbon groups having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

[0093] Examples of aromatic hydrocarbon groups include unsubstituted aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; and aryl groups such as alkyl group-substituted aryl groups, such as a tolyl group, a dimethylphenyl group, an isopropylphenyl group, a t-butylphenyl group, or a di-t-butylphenyl group.

[0094] The hydrocarbon group may have at least one hydrogen atom substituted with another hydrocarbon group. Examples of the hydrocarbon group having at least one hydrogen atom substituted with another hydrocarbon group include aryl-substituted alkyl groups such as benzyl and cumyl groups, and cyclic saturated hydrocarbon-substituted alkyl groups such as cyclohexylmethyl groups.

[0095] Examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0096] Examples of the neutral conjugated or non-conjugated dienes include neutral conjugated or non-conjugated dienes having 4 to 20 carbon atoms. Specifically, s-cis- or s-trans-η 4 -1,3-butadiene, s-cis- or s-trans-η 4 -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η 4 -3-Methyl-1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-Dibenzyl-1,3-butadiene, s-cis- or s-trans-η 4 -2,4-Hexadiene, s-cis- or s-trans-η 4 -1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-Ditolyl-1,3-butadiene, s-cis- or s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene.

[0097] Examples of the anionic ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; and phosphine imide groups such as tri(tert-butyl)phosphine imide and tridamantylphosphine imide.

[0098] Examples of neutral ligands capable of coordinating with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, dioxane, diethyl ether, and 1,2-dimethoxyethane.

[0099] In general formulas (B1) to (B3), j represents an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2 or 3. When j is an integer of 2 or greater, multiple Qs may be the same or different.

[0100] In the general formulas (B1) and (B2), Cp 1 and Cp 2 may be the same or different and represent a cyclopentadienyl group or a substituted cyclopentadienyl group capable of forming a sandwich structure together with M. A substituted cyclopentadienyl group is a group in which at least one hydrogen atom of a cyclopentadienyl group has been substituted with a substituent.

[0101] Examples of the substituent in the substituted cyclopentadienyl group include a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms, hereinafter sometimes referred to as a "hydrocarbon group (f1)") and a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms, hereinafter sometimes referred to as a "silicon-containing group (f2)"). Other examples of the substituent in the substituted cyclopentadienyl group include heteroatom-containing groups (excluding the silicon-containing group (f2)) such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups.

[0102] The hydrocarbon group (f1) is preferably a hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include linear or branched hydrocarbon groups (e.g., alkyl groups, alkenyl groups, alkynyl groups), cyclic saturated hydrocarbon groups (e.g., cycloalkyl groups), and cyclic unsaturated hydrocarbon groups (e.g., aryl groups). The hydrocarbon group (f1) also includes groups in which any two hydrogen atoms bonded to adjacent carbon atoms among the above-mentioned groups are simultaneously substituted to form an alicyclic or aromatic ring.

[0103] Specific examples of the hydrocarbon group (f1) include linear aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, and allyl groups; isopropyl, isobutyl, sec-butyl, t-butyl, amyl, 3-methylpentyl, neopentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, and 1,1-dimethyl branched aliphatic hydrocarbon groups such as 1-methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group, and alkyl-substituted versions of these groups; and groups in which at least one hydrogen atom of a saturated hydrocarbon group has been substituted with an aryl group, such as benzyl group and cumyl group.

[0104] The silicon-containing group (f2) is preferably a silicon-containing group having 1 to 20 carbon atoms, and examples thereof include groups in which a silicon atom is directly covalently bonded to a ring carbon of a cyclopentadienyl group, and specific examples thereof include alkylsilyl groups (e.g., trimethylsilyl group) and arylsilyl groups (e.g., triphenylsilyl group).

[0105] Specific examples of the heteroatom-containing group (excluding the silicon-containing group (f2)) include a methoxy group, an ethoxy group, a phenoxy group, an N-methylamino group, a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

[0106] Among the hydrocarbon groups (f1), preferred examples include linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, n-butyl, n-hexyl, isopropyl, isobutyl, sec-butyl, t-butyl, and neopentyl groups.

[0107] The substituted cyclopentadienyl group includes an indenyl group, a fluorenyl group, an azulenyl group, and groups in which one or more hydrogen atoms of these groups have been substituted with the above-mentioned hydrocarbon groups (including groups in which any two hydrogen atoms bonded to adjacent carbon atoms are simultaneously substituted to form an alicyclic or aromatic ring), and in the case of an indenyl group, a fluorenyl group, or an azulenyl group, part or all of the double bonds of the unsaturated ring fused to the cyclopentadienyl group may be hydrogenated.

[0108] In the general formula (B2), Y represents a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO2-, -Ge-, -Sn-, or -NR a -, -P(R a )-, -P(O)(R a )-, -BR a -or- AlR a - indicates that R a is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a hydrogen atom, a halogen atom, or a nitrogen atom (-NRH or -NR2; R is a hydrocarbon group having 1 to 20 carbon atoms).

[0109] Further examples of the metallocene compound represented by general formula (B2) include a bridged metallocene compound represented by the following general formula (B2a) (hereinafter also referred to as "bridged metallocene compound (B2a)"), as disclosed in WO 01 / 27124.

[0110] [ka]

[0111] The bridged metallocene compound (B2a) has the following structural features [m1] to [m3]. [m1] Of the two ligands, one is a cyclopentadienyl group which may have a substituent, and the other is a fluorenyl group which may have a substituent. [m2] The two ligands are bonded by a covalent bridge portion (hereinafter also referred to as a "bridge portion") consisting of a carbon atom or a silicon atom. [m3] The transition metal (M) constituting the metallocene compound is an atom of Group 4 of the periodic table, specifically, a titanium atom, a zirconium atom, or a hafnium atom. The cyclopentadienyl group, fluorenyl group, crosslinking portion and other features of the bridged metallocene compound (B2a) will be explained below in order.

[0112] (cyclopentadienyl group) In general formula (B2a), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group, and is preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group, and two adjacent groups may be bonded to each other to form a ring.

[0113] For example, R 1 , R 2 , R 3 and R 4 are all hydrogen atoms or R 1 , R 2 , R 3 and R 4At least one of the above is a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms) or a silicon-containing group (preferably a silicon-containing group having 1 to 20 carbon atoms). Other examples include heteroatom-containing groups such as halogenated hydrocarbon groups, oxygen-containing groups, and nitrogen-containing groups.

[0114] R 1 , R 2 , R 3 and R 4 When two or more of R are substituents other than hydrogen atoms, the substituents may be the same or different; 1 , R 2 , R 3 and R 4 Any two adjacent groups among these may be bonded to each other to form an alicyclic or aromatic ring.

[0115] R 1 ~R 4 Examples and preferred hydrocarbon groups in R include the hydrocarbon groups (f1) defined above in the section on the substituted cyclopentadienyl group. 1 ~R 4 Examples and preferred examples of the silicon-containing group in R include the silicon-containing group (f2) defined above in the section on the substituted cyclopentadienyl group. 1 ~R 4 Examples of the heteroatom-containing group in include the groups exemplified above for the substituted cyclopentadienyl group.

[0116] (fluorenyl group) In general formula (B2a), R 5 , R 8 , R 9 and R 12 R each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group, and is preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group. 6 and R 11are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group; R 7 and R 10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and are preferably a hydrogen atom, a hydrocarbon group, or a silicon-containing group; R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring.

[0117] From the viewpoint of polymerization activity, R 6 and R 11 are not all hydrogen atoms, or R 7 and R 10 is preferably not a hydrogen atom, and R 6 , R 7 , R 10 and R 11 It is more preferable that none of R 6 and R 11 are the same group selected from hydrocarbon groups and silicon-containing groups, or R 7 and R 10 It is particularly preferred that R are the same group selected from hydrocarbon groups and silicon-containing groups. 6 and R 7 are bonded to each other to form an alicyclic or aromatic ring, and R 10 and R 11 are most preferably bonded to each other to form an alicyclic or aromatic ring.

[0118] R 5 ~R 12 Examples and preferred hydrocarbon groups in R include the hydrocarbon groups (f1) defined above in the section on the substituted cyclopentadienyl group. 5 ~R 12Examples and preferred examples of the silicon-containing group in R include the silicon-containing group (f2) defined above in the section on the substituted cyclopentadienyl group. 5 ~R 12 Examples of the heteroatom-containing group in include the groups exemplified above for the substituted cyclopentadienyl group.

[0119] R 6 and R 7 (R 10 and R 11 ) are bonded to each other to form an alicyclic or aromatic ring, suitable examples of the substituted fluorenyl group include groups having structures derived from compounds represented by the general formulae [I] to [V] described below.

[0120] (Bridge part) In general formula (B2a), R 13 and R 14 Each of the bridging atoms Y in the bridging portion independently represents an alkyl group or an aryl group, and Y represents a carbon atom or a silicon atom. The bridging atoms Y in the bridging portion may be the same or different alkyl groups or aryl groups [R 13 and R 14 ] is bonded. Furthermore, R 13 and R 14 may be bonded to each other to form a ring structure.

[0121] Examples of the alkyl group include the hydrocarbon group (f1) defined above in relation to the substituted cyclopentadienyl group. 13 and R 14 As a ring structure in which these are bonded to each other, Y 1 When is a carbon atom, examples of the aryl group include a cyclohexyl group and a cyclopentyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and groups in which one or more of the aromatic hydrogens (sp2 hydrogens) contained in these groups are substituted with a substituent. Examples of the substituent include the hydrocarbon group (f1) and silicon-containing group (f2) defined above in the section on the substituted cyclopentadienyl group, as well as halogen atoms and halogenated hydrocarbon groups.

[0122] Specific examples of aryl groups include unsubstituted aryl groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, anthracenyl, and biphenyl; alkyl-substituted aryl groups such as tolyl, dimethylphenyl, isopropylphenyl, n-butylphenyl, and t-butylphenyl; cycloalkyl-substituted aryl groups such as cyclohexylphenyl; halogenated aryl groups such as chlorophenyl, bromophenyl, dichlorophenyl, and dibromophenyl; halogenated alkyl-substituted aryl groups such as (trifluoromethyl)phenyl and bis(trifluoromethyl)phenyl; and oxygen-containing group-substituted aryl groups such as p-methoxyphenyl. The positions of the substituents are preferably meta and / or para positions. Among these, substituted phenyl groups in which the substituents are located at the meta and / or para positions are more preferred.

[0123] [Other Features of Bridged Metallocene Compounds] In general formula (B2a), Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or greater, multiple Qs may be the same or different.

[0124] Examples of the halogen atom, hydrocarbon group, halogenated hydrocarbon group, neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, anionic ligand, or neutral ligand capable of coordinating with a lone electron pair in Q include the same atoms or groups as those exemplified for Q in the general formulae (B1) to (B3) above.

[0125] Specific examples of the bridged metallocene compound (B2a) are shown below, but the scope of the present invention is not particularly limited by these. Among the example compounds, octamethyloctahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [I], octamethyltetrahydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [II], dibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [III], 1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [IV], 1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [V], and tetramethyldodecahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [VI].

[0126] [ka]

[0127] Specific examples of the metallocene compounds represented by general formula (B1) or (B2) (for example, (B2a)) include the compounds listed in paragraphs

[0078] to

[0079] of WO 2013 / 161833 and the compounds listed in paragraphs

[0259] to

[0262] of WO 2014 / 123212.

[0128] A preferred example of the bridged metallocene compound (B2) is a compound (B2b) represented by the following general formula (B2b).

[0129] [ka]

[0130] (R 1 From R 16 ) In general formula (B2b), R 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 1 From R 16 Any two of the substituents may be bonded to each other to form a ring.

[0131] R 1 ~R 16 The hydrocarbon group, heteroatom-containing hydrocarbon group, and silicon-containing group in the general formula (B2a) are R 1 ~R 14 Examples of the hydrocarbon groups, heteroatom-containing hydrocarbon groups, and silicon-containing groups are those exemplified as above.

[0132] R 1 ~R 16 Among the substituents up to 1 and R 2 , R 2 and R 3 , R 4 and R 6 , R 4 and R 7 , R 5 and R 6 , R 5 and R 7 , R 6 and R 8 , R 7 and R 8 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , R 15 and R16 ) may be bonded to each other to form a ring, and R 4 and R 5 may be bonded to each other to form a ring, and R 6 and R 7 may be bonded to each other to form a ring, and R 1 and R 8 may be bonded to each other to form a ring, and R 3 and R 4 may be bonded to each other to form a ring, and R 3 and R 5 may be bonded to each other to form a ring. The ring formation may occur at two or more positions in the molecule.

[0133] In this specification, examples of the ring (additional ring) formed by bonding two substituents together include an alicyclic ring, an aromatic ring, and a heterocyclic ring.Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, a cyclopentene ring, a heterocyclic ring such as a furan ring, a thiophene ring, and the like, and corresponding hydrogenated heterocyclic rings, and preferred are a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring.Furthermore, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0134] R 1 and R 3 is preferably a hydrogen atom. R 2 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, more preferably a hydrocarbon group, even more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, particularly preferably a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic saturated hydrocarbon group, and particularly preferably a substituent in which the carbon having a free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon.

[0135] R 2Specific examples of the substituent include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group, more preferably a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, and particularly preferably a 1-adamantyl group or a tert-butyl group.

[0136] R 4 is one of the preferred embodiments in which, when the transition metal complex (B) is represented by the following general formula (B2b'), is a hydrogen atom.

[0137] [ka]

[0138] In this case, the transition metal complex (B) includes all enantiomers of the transition metal complex represented by the general formula (B2b'), for example, the transition metal complex represented by the following general formula (B2b"), within the scope of the present invention.

[0139] [ka]

[0140] In the notation of general formula (B2b') and (B2b"), MQ j The part is assumed to be in front of the paper and the bridge part is assumed to be in the back of the paper. That is, in these transition metal complexes, the α-position of the cyclopentadiene ring (based on the carbon atom substituted by the bridge part) has a hydrogen atom (R 4 ) exists.

[0141] On the other hand, in the above-mentioned general formula (B2b), MQ j It is not specified whether the portion and the crosslinked portion are present in front of or behind the paper. In other words, the compound (B2b) represented by the general formula (B2b) includes a transition metal complex of a specific structure and its enantiomer.

[0142] R 4 , R 5 , R 6 and R 7 At least one selected from R is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, 4 and R 5 is more preferably a hydrogen atom or a hydrocarbon group, and R 5 is more preferably an alkyl group such as a linear alkyl group or a branched alkyl group, a cycloalkyl group, or a cycloalkenyl group, and is particularly preferably an alkyl group having 1 to 10 carbon atoms. 4 and R 5 In one preferred embodiment, both of R are alkyl groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferred. 6 and R 7 It is also preferred that R is a hydrogen atom. 5 and R 7 are more preferably bonded to each other to form a ring, and the ring is particularly preferably a six-membered ring such as a cyclohexane ring.

[0143] R 8 is preferably a hydrocarbon group, and particularly preferably an alkyl group such as a methyl group. In the general formula (B2b), the fluorene ring portion is not particularly limited as long as it has a structure obtained from a known fluorene derivative. 9 , R 12 , R 13 and R 16 is preferably a hydrogen atom.

[0144] R 10 , R 11 , R 14 and R 15is preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group, or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms, such as a 2,7-di-tert-butylfluorenyl group, a 3,6-di-tert-butylfluorenyl group, or a 2,7-diphenyl-3,6-di-tert-butylfluorenyl group, and particularly preferably a 2,7-di-tert-butylfluorenyl group.

[0145] R 10 and R 11 are bonded to each other to form a ring, and R 14 and R 15 may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, a 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydro-12H-dibenzo[b,h]fluorenyl group (the octamethyloctahydrodibenzofluorenyl group represented by the formula [I]), a 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, a 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group, a 4,4,7,7-tetramethyl Examples thereof include a 1,1,4,4,7,7,10,10-dodecahydro-12H-dibenzo[b,h]fluorenyl group (a tetramethyldodecahydrodibenzofluorenyl group represented by the formula [VI]), and particularly preferred examples include a 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydro-12H-dibenzo[b,h]fluorenyl group (an octamethyloctahydrodibenzofluorenyl group represented by the formula [I]) and a 4,4,7,7-tetramethyl-1,2,3,4,7,8,9,10-dodecahydro-12H-dibenzo[b,h]fluorenyl group (a tetramethyldodecahydrodibenzofluorenyl group represented by the formula [VI]).

[0146] (M, Q, j) In the general formula (B2b), M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

[0147] Q is a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. Examples of the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with a lone electron pair in Q include those exemplified as the halogen atom, hydrocarbon group, anionic ligand, and neutral ligand capable of coordinating with a lone electron pair in the above-mentioned general formula (B2a).

[0148] j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected from the same or different combinations. Specific examples of the compound (B2b) include the compounds listed on pages 11 to 15 of WO 2006 / 68308, the compounds listed in

[0075] to

[0086] of WO 2014 / 50816, and the compounds listed in

[0072] to

[0084] of JP 2008 / 045008 A.

[0149] More specifically, the metallocene compounds represented by the general formulae (B1) to (B3) are more preferably metallocene compounds represented by the following general formulae (B1-1), (B2-1) to (B2-3), and (B3-1).

[0150] [ka]

[0151] Examples of the transition metal complex (B) include compounds (B4) represented by the following general formula (B4), as described in JP-A-11-315109, JP-A-2000-239312, WO 2001 / 55231, and Chemical Review, Vol. 111, pages 2363-2449, 2011.

[0152] [ka]

[0153] In the general formula (B4), M represents a transition metal atom of Groups 4 to 10 of the periodic table, m represents an integer of 1 to 6; R 19 ~R 24 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring; Also, when m is 2 or more, R 19 ~R 24 Two of the groups represented by the formula may be linked together, n is a number that satisfies the valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other to form a ring.

[0154] Specific examples include bis{N-(5-adamantyl-3-methylsalicylidene)-2-methylcyclohexylaminato}zirconium(IV) dichloride and bis{N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato}titanium(IV) dichloride.

[0155] Examples of the transition metal complex (B) include compounds (B5) represented by the following general formula (B5), as described in WO 2009 / 5003, JP 2011-178682 A, and JP 2011-195584 A.

[0156] [ka]

[0157] In general formula (B5), R 25 ~R 30 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other. 25 may be linked to Z.

[0158] M represents a transition metal atom selected from Groups 3 to 10 of the periodic table. n indicates the valence of M. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and the atoms and groups represented by X may be the same or different from one another, and the groups represented by X may be bonded to one another to form a ring.

[0159] Y represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom. Z represents a hydrocarbon group or a heterocyclic compound residue which may have a substituent, and the minimum number of bonds connecting Y and N is 4 to 6.

[0160] The bond connecting Y and Z may be a double bond or a triple bond, and Y and R 25 The bond connecting the two may be a double bond or a triple bond. In the formula, the dotted line indicates a coordinate bond. The compound (B5) represented by the general formula (B5) includes trichloro{6-[(2'-methoxy-κO 1 -biphenyl-2-yl)imino-κN 1 -methyl]-4-methyl-2-(tricyclo[3.3.1.1 3,7]decan-1-yl)phenolato}titanium(IV).

[0161] Examples of the transition metal complex (B) include the compound (B6) represented by the following general formula (B6), which is described in US Pat. No. 5,272,236. L 1 M 1 X n …(B6) In general formula (B6), M 1 is a metal in Group 4 of the periodic table or the lanthanide series, L 1 is a derivative of a delocalized π-bonded group, and the metal M 1 It provides a constrained geometry at the active site, Each X is independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group, or a germyl group.

[0162] n is an integer of 1 to 2, and is selected depending on the valence of M and the type of X so that the compound (B6) as a whole is electrically neutral. Among the compounds (B6), the compounds represented by the following general formula (B6a) are preferred.

[0163] [ka]

[0164] In general formula (B6a), M 1 is titanium, zirconium or hafnium, and X is the same as above. Cp is M 1 and a substituted cyclopentadienyl group having a substituent Z. Z is oxygen, sulfur, boron, or an element of Group 14 of the periodic table (e.g., silicon, germanium, or tin), and Y is a ligand containing nitrogen, phosphorus, oxygen, or sulfur, and Z and Y may form a fused ring.

[0165] Specific examples of the compound represented by the general formula (B6a) include [dimethyl(t-butylamido)(tetramethyl-η 5Compounds described in

[0062] of JP-T-2017-511396 such as (cyclopentadienyl) silane titanium dichloride, and in these compounds, compounds in which titanium is replaced with zirconium or hafnium, and in these compounds, two Xs in the above formula (B6a) are replaced with one conjugated or non-conjugated diene (for example, s-cis- or s-trans-η 4 -1,3-pentadiene), and compounds obtained by replacing them. The transition metal complex (B) may be used alone or in combination of two or more.

[0166] <Compound (C)> The olefin polymerization catalyst of the present invention preferably contains the following compound (C). Compound (C) (hereinafter sometimes referred to as "component (C)") is (C-1) an organometallic compound (hereinafter also referred to as "component (C-1)"), preferably an organoaluminum compound (C-1a) represented by the following general formula (C-1a), a complex alkylated product (C-1b) of a Group 1 metal and aluminum represented by the following general formula (C-1b), or a dialkyl compound (C-1c) of a Group 2 or Group 12 metal represented by the following general formula (C-1c), R a m Al(OR b ) n H p X q … (C-1a) [In the general formula (C-1a), R a and R b each represents a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m is a number of 0 < m ≦ 3, n is a number of 0 ≦ n < 3, p is a number of 0 ≦ p < 3, q is a number of 0 ≦ q < 3, and m + n + p + q = 3. ] M a AlR a 4… (C-1b) [In the general formula (C-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 (preferably 1 to 4) carbon atoms. ] R a r M b R b s X t … (C-1c) [In general formula (C-1c), R a and R b represent hydrocarbon groups having 1 to 15 carbon atoms, and may be the same or different from each other; M b is selected from Mg, Zn and Cd, X represents a halogen atom, and r is 0. <r≦2、sは0≦s≦1、tは0≦t≦1であり、かつr+s+t=2である。〕、および (C-2) At least one compound selected from the group consisting of organoaluminum oxy compounds (hereinafter also referred to as "component (C-2)").

[0167] 《Organometallic compound (C-1)》 The organoaluminum compound (C-1a) is tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum; tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tri(4-methylphenyl)aluminum; dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylaluminum hydride, and diisobutylaluminum hydride; General formula (i-C4H9) x Al y (C5H 10 ) z(wherein x, y, and z are positive numbers, and z≦2x), alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; General formula R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the following formula: alkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride; Alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride and other partially hydrogenated alkyl aluminums; Examples of the aluminum compounds include partially alkoxylated and halogenated alkyl aluminum compounds such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, and ethyl aluminum ethoxy bromide. a m Al(OR b )n H p X q Compounds similar to the compound represented by the formula (1) can also be used, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0168] Examples of the alkylated complexes of Group 1 metals and aluminum (C-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned. Examples of the dialkyl compounds (C-1c) of Group 2 or Group 12 metals include dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, ethyl-n-butyl magnesium, diphenyl magnesium, dimethyl zinc, diethyl zinc, di-n-butyl zinc, and diphenyl zinc. Among these, the organoaluminum compound (C-1a) is preferred. The organometallic compound (C-1) may be used alone or in combination of two or more kinds.

[0169] 《Organoaluminum oxy compound (C-2)》 The organoaluminum oxy compound (C-2) may be, for example, a conventionally known aluminoxane, or an organoaluminum oxy compound that is insoluble or poorly soluble in benzene, such as those exemplified in JP-A-2-78687. Conventionally known aluminoxanes can be produced, for example, by the following methods (1) to (4), and are usually obtained as a solution in a hydrocarbon solvent.

[0170] (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound.

[0171] (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

[0172] (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0173] (4) A method in which an organoaluminum such as trialkylaluminum is reacted with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, a ketone, or a carboxylic acid, and the resulting compound is subjected to a non-hydrolytic conversion such as thermal decomposition reaction.

[0174] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0175] Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound (C-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0176] Other examples of organoaluminum oxy compounds (C-2) include modified methylaluminoxanes. Modified methylaluminoxanes are aluminoxanes prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. MMAO can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584. Tosoh Finechem Corporation and other companies also commercially produce aluminoxanes prepared using trimethylaluminum and triisobutylaluminum, where R is an isobutyl group, under the names MMAO and TMAO.

[0177] Such MMAOs are aluminoxanes with improved solubility in various solvents and improved storage stability. Specifically, unlike the above-mentioned MMAOs that are insoluble or poorly soluble in benzene, they are characterized by their solubility in aliphatic hydrocarbons and alicyclic hydrocarbons.

[0178] Further examples of the organoaluminum oxy compound (C-2) include organoaluminum oxy compounds containing a boron atom, halogen-containing aluminoxanes such as those exemplified in WO 2005 / 066191 and WO 2007 / 131010, and ionic aluminoxanes such as those exemplified in WO 2003 / 082879. The organoaluminum oxy compound (C-2) may be used alone or in combination of two or more kinds.

[0179] <Organic compound component (D)> The olefin polymerization catalyst of the present invention may further contain an organic compound component (D). The organic compound component (D) is used as needed to improve the polymerization performance and the physical properties of the resulting polymer. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0180] [Olefin polymerization catalyst / method for producing olefin polymers] Examples of the method for producing the olefin polymerization catalyst of the present invention include the following methods (1) to (3). Hereinafter, compound (A), transition metal complex (B), and, if necessary, compound (C), and organic compound component (D) will be referred to as "component (A)," "component (B)," "component (C)," and "component (D)," respectively. (1) A method in which components (A) and (B) are added to a polymerization reactor in any order. (2) A method in which components (A), (B), and (C) are added to a polymerization reactor in any order. (3) A method in which components (A), (B), (C), and (D) are added to a polymerization reactor in any order.

[0181] The method for producing an olefin polymer of the present invention is characterized by comprising a step [P] of polymerizing an olefin (such as ethylene or an α-olefin having 3 to 20 carbon atoms) in the presence of the above-mentioned olefin polymerization catalyst. Here, "polymerization" is a general term for homopolymerization and copolymerization. Furthermore, "polymerizing an olefin in the presence of an olefin polymerization catalyst" encompasses embodiments in which each component of the olefin polymerization catalyst is added to a polymerization vessel by any method, such as the above-mentioned methods (1) to (3), to polymerize the olefin.

[0182] In the olefin polymer production method of the present invention, polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Furthermore, a so-called bulk polymerization method can also be used, in which the liquefied olefin to be supplied to the polymerization itself is used as the solvent.

[0183] The compound (A) allows the transition metal complex (B) to be immobilized to the compound (A) at a higher rate than when a compound conventionally used as a co-catalyst in olefin polymerization is used instead of the compound (A). Therefore, the method for producing an olefin polymer of the present invention makes it possible to produce an olefin polymer with high activity even in a suspension polymerization method or a gas-phase polymerization method, which was difficult when a conventional compound containing a Group 13 element (e.g., a borate compound) was used.

[0184] When olefins are polymerized using an olefin polymerization catalyst, the amounts of each component that can constitute the olefin polymerization catalyst are as follows. In addition, the contents of each component in the olefin polymerization catalyst can be adjusted as follows.

[0185] Compound (A) (component (A)) can be used in an amount such that the molar ratio of component (A) to the total transition metal atoms (M) in component (B) [(A) / (M)] is generally 1 to 100, preferably 1 to 20. When the molar ratio is within this range, the proportion of component (A) having two or more sites that come into contact with component (B) is low, and component (A) has low affinity with hydrocarbon media when the olefin polymerization catalyst is used in a hydrocarbon medium, resulting in excellent catalyst immobilization and activation performance.

[0186] Component (B) is usually 1 x 10 per liter of reaction volume. -10 ~1×10 -2 mol, preferably 1 x 10 -8 ~1×10 -3 It is used in molar amounts. When component (C-1) is used, it can be used in an amount such that the molar ratio of component (C-1) to the total transition metal atoms (M) in component (B) [(C-1) / (M)] is generally 1 to 50,000, preferably 10 to 20,000, and particularly preferably 50 to 10,000.

[0187] When component (C-2) is used, it can be used in an amount such that the molar ratio [Al / (M)] of aluminum atoms in component (C-2) to the total transition metal atoms (M) in component (B) is generally 10 to 5,000, preferably 20 to 2,000.

[0188] In the method for producing an olefin polymer of the present invention, the polymerization temperature is usually -50 to +200°C, preferably 0 to 200°C, and more preferably 40 to 150°C, and the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, and preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen or the like to the polymerization system, changing the polymerization temperature, or by the amount of component (C) used.

[0189] Hydrogen, in particular, is a preferred additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the appropriate amount is approximately 0.00001 to 100 NL per mole of olefin. The hydrogen concentration in the system can be adjusted not only by adjusting the amount of hydrogen supplied, but also by performing a reaction that produces or consumes hydrogen within the system, by separating hydrogen using a membrane, or by releasing some of the hydrogen-containing gas outside the system.

[0190] The olefin polymer (e.g., ethylene / α-olefin / non-conjugated polyene copolymer) obtained by the method for producing an olefin polymer of the present invention may be subjected to known post-treatment steps such as a catalyst deactivation step, a catalyst residue removal step, a drying step, etc., as needed, after the olefin polymer is synthesized by the above-mentioned method.

[0191] In one embodiment of the method for producing an olefin polymer of the present invention, the olefin supplied to the polymerization reaction includes ethylene and an α-olefin having 3 to 20 carbon atoms.

[0192] In this embodiment, ethylene may be homopolymerized, ethylene may be copolymerized with an α-olefin having 3 to 20 carbon atoms, or an α-olefin having 3 to 20 carbon atoms may be homopolymerized or copolymerized.

[0193] Examples of the α-olefin include linear or branched α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and vinylcyclohexane. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, such as a linear or branched α-olefin having 3 to 10 carbon atoms, more preferably propylene, 1-butene, 1-hexene, and 1-octene, and even more preferably propylene. These α-olefins may be used alone or in combination of two or more.

[0194] Furthermore, a non-conjugated polyene may be copolymerized together with ethylene or an α-olefin having 3 to 20 carbon atoms.

[0195] It is believed that when compound (A) is brought into contact with transition metal complex (B), the transition metal complex (B), which is the main catalyst, is activated, and the amine moiety coordinates with the polymerization active species, thereby immobilizing transition metal complex (B) on compound (A).

[0196] In the production of olefin polymers by polymerizing olefins in the presence of an olefin polymerization catalyst obtained by contacting a transition metal complex with a Group 13 element-containing compound, when compound (A) is used as the Group 13 element-containing compound, the size of the substituent in the anion moiety is larger than that of conventional Group 13 element-containing compounds (e.g., Group 13 element-containing compound (A'-1) described below). In particular, introducing a large-sized substituent into the meta position has the effect of lengthening the interionic distance in the ion pair consisting of the cation of the transition metal complex and the anion (β-1), and it is thought that this corresponding weakening of the interionic interaction improves the catalytic performance. [Example]

[0197] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0198] <Measurement method> [Identification of Group 13 element-containing compound (A)] The structure of the group 13 element-containing compound is 270MHz 1 H-NMR (GSH-270 manufactured by JEOL Ltd.), 160MHz 11 Measurement was carried out using B-NMR (ECA-500 manufactured by JEOL Ltd.) and the like, and various signals were assigned and determined according to standard methods.

[0199] [Polymer weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC) using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph) under the following operating conditions: (Operating conditions) Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, manufactured by Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, manufactured by Tosoh Corporation) Mobile phase: o-dichlorobenzene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (built into the device) Column temperature: 140℃ Flow rate: 1.0mL / min Injection volume: 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation) / molecular weight 495 to 20.6 million

[0200] <Synthesis of Group 13 element-containing compounds> [Manufacturing Example 1] (Synthesis of anion precursor (compound (a-1))) In Production Examples 1 and 2, triphenylmethyl chloride was purchased from Fujifilm Wako Pure Chemical Industries, Ltd., 1-bromo-3,5-dichloro-2,4,6-trifluorobenzene was purchased from Matrix Scientific, Inc., 1.6 M n-butyllithium / hexane solution was purchased from Kanto Chemical Co., Inc., and 1.0 M boron tribromide / heptane solution was purchased from Aldrich, and all of these were used as they were. A 200 mL reactor was thoroughly dried and purged with nitrogen, and 2.0 g of 1-bromo-3,5-dichloro-2,4,6-trifluorobenzene and 30 mL of diethyl ether were added and stirred. The mixture was then cooled to -78°C, and 4.5 mL (1.0 equivalent) of a 1.6 M n-butyllithium / hexane solution was slowly added dropwise, followed by stirring for 1 hour. 2.1 mL (0.25 equivalent) of a 1.0 M boron tribromide / heptane solution was slowly added dropwise, and the mixture was stirred overnight while slowly warming to room temperature. The diethyl ether was then removed under reduced pressure, and the resulting suspension was dissolved in 10 mL of dichloromethane. The insoluble matter in the resulting suspension was removed by passing it through Celite on a glass filter, and the solvent was distilled off. The residue was washed with hexane, filtered, and dried under reduced pressure to obtain 600 mg (41% yield) of compound (a-1) represented by the following formula (a-1). 11 B-NMR(CDCl3)δ -16.79 ppm

[0201] [ka]

[0202] [Manufacturing Example 2] (Synthesis of Group 13 element-containing compound (A-1)) A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 240 mg of compound (a-1) obtained in Preparation Example 1 and 20 mL of dichloromethane and stirred. The mixture was then cooled in an ice bath, and a solution of 120 mg (1.5 equivalents) of triphenylmethyl chloride dissolved in 10 mL of dichloromethane was added dropwise. The mixture was stirred overnight while slowly warming to room temperature. The insoluble matter in the resulting suspension was then removed by passing it through Celite on a glass filter, and the solvent was distilled off. The residue was washed with a dichloromethane / hexane (1:1) mixed solvent and then with hexane, and dried under reduced pressure to obtain 150 mg (50% yield) of Group 13 element-containing compound (A-1) represented by the following formula (A-1). 1 H-NMR(tol-d8)δ 7.62(6H),7.82(6H),8.22(3H)ppm

[0203] [ka]

[0204] [Manufacturing Example 3] (Synthesis of cation precursor (compound (a-2))) In Production Example 3, N,N-dimethylaniline and hydrogen chloride (approximately 1 mol / L diethyl ether solution) were purchased from Tokyo Chemical Industry Co., Ltd. and used as they were. A 50 mL reactor was thoroughly dried and purged with nitrogen, and 3.4 g of N,N-dimethylaniline and 10 mL of diethyl ether were added and stirred. Then, 25 mL of a 1 M hydrogen chloride / diethyl ether solution was added dropwise in an ice bath, and the mixture was allowed to warm to room temperature and stirred for 1 hour. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 2.6 g (yield 99%) of compound (a-2) represented by the following formula (a-2). 1 H-NMR(CDCl3)δ 3.17(6H),7.47-7.49(3H),7.76-7.79(2H),14.51(NH)ppm

[0205] [ka]

[0206] [Manufacturing Example 4] (Synthesis of Group 13 element-containing compound (A-2)) A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 180 mg of compound (a-1) obtained in Preparation Example 1 and 10 mL of dichloromethane and stirred. A solution of 35 mg (1.0 equivalent) of compound (a-2) obtained in Preparation Example 3 dissolved in 10 mL of dichloromethane was added dropwise and stirred overnight at room temperature. The insoluble matter in the resulting suspension was then removed by passing it through Celite on a glass filter, and the solvent was distilled off. The residue was washed with water and then hexane and dried under reduced pressure to obtain 150 mg (71% yield) of the Group 13 element-containing compound (A-2) represented by the following formula (A-2). 1 H-NMR(tol-d8)δ 2.22(6H),6.51(2H),6.75(1H),7.01(2H)ppm

[0207] [ka]

[0208] [Manufacturing Example 5] (Synthesis of Group 13 Element-Containing Compound (A-5)) In Production Examples 5 and 6, 1,4-diazabicyclo[2.2.2]octane dihydrochloride was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as is. In a thoroughly dried, nitrogen-purged 50 mL reactor, 220 mg of compound (a-1) obtained in Preparation Example 1 and 5 mL of dichloromethane were added and stirred. Then, a solution of 50 mg (1.0 equivalent) of 1,4-diazabicyclo[2.2.2]octane dihydrochloride in 10 mL of dichloromethane was added dropwise, and stirring was continued at room temperature for 24 hours. The insoluble matter in the resulting suspension was removed by passing it through Celite on a glass filter, and the solvent was distilled off. The residue was washed with water, hexane, and dichloromethane, respectively, and the insoluble matter was collected by filtration and dried under reduced pressure to obtain 160 mg (yield 63%) of a Group 13 element-containing compound represented by the following formula (A-5). 1H NMR(CD3OD) δ 3.31(12H,s)ppm

[0209] [ka]

[0210] [Manufacturing Example 6] (Synthesis of Group 13 Element-Containing Compound (A'-5)) In Production Example 6, lithium tetrakis(pentafluorophenyl)borate ethyl ether complex was purchased from Tokyo Chemical Industry Co., Ltd. and used as it was. A 200 mL reactor was thoroughly dried and purged with nitrogen, and 2.7 g of lithium tetrakis(pentafluorophenyl)borate ethyl ether complex and 80 mL of dichloromethane were added and stirred. A solution of 0.5 g of 1,4-diazabicyclo[2.2.2]octane dihydrochloride in 20 mL of dichloromethane was then added dropwise, and the mixture was stirred at room temperature for 24 hours. The insoluble material in the resulting suspension was removed by passing it through Celite on a glass filter, and the solvent was evaporated. The residue was washed with water, hexane, and dichloromethane, respectively. The insoluble material was collected by filtration and dried under reduced pressure to obtain 1.9 g (85% yield) of a Group 13 element-containing compound represented by the following formula (A'-5). 1 H NMR(CD3OD) δ 3.34(12H,s)ppm

[0211] [ka]

[0212] <Preparation of polymerization catalysts using Group 13 element-containing compounds and evaluation of atmospheric pressure ethylene polymerization> The Group 13 element-containing compounds (A'-1), (A'-2), and (A'-5) used in the comparative examples are as follows. ·Compounds containing Group 13 elements (A'-1) Triphenylcarbenium tetrakis(pentafluorophenyl)borate represented by the following formula (A'-1) was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0213] [ka]

[0214] ·Compounds containing Group 13 elements (A'-2) N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate represented by the following formula (A'-2) was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0215] [ka]

[0216] ·Compounds containing Group 13 elements (A'-5) The compound represented by the formula (A'-5) obtained in Production Example 6 was used.

[0217] As the transition metal complex (B), transition metal complexes (B1-1), (B2-1) to (B2-3), and (B3-1) represented by the following formulae (B1-1), (B2-1) to (B2-3), and (B3-1), which were produced by conventionally known methods, were used.

[0218] [ka]

[0219] [Example 1] 250 mL of toluene was added to a 500 mL glass reactor thoroughly purged with nitrogen. Ethylene was then introduced at 100 L / hr to saturate the reactor with ethylene. Polymerization was then initiated by adding 0.20 mmol of triisobutylaluminum, 0.500 μmol of the transition metal complex (B2-1), and 4 equivalents (2.000 μmol) of the Group 13 element-containing compound (A-1) obtained in Production Example 2 relative to the transition metal complex (B2-1). Ethylene was continuously introduced at 100 L / hr, and polymerization was carried out at 50°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by the addition of a small amount of methanol. After polymerization, the reaction mixture was added to 1 L of methanol containing a small amount of hydrochloric acid to precipitate an olefin polymer. The resulting mixture was filtered and dried under reduced pressure at 80°C for 10 hours, yielding 2.04 g of olefin polymer. The Mw of the resulting olefin polymer was 228,000.

[0220] [Comparative Example 1] Polymerization was carried out in the same manner as in Example 1, except that the Group 13 element-containing compound (A'-1) was used instead of the Group 13 element-containing compound (A-1), to obtain 1.48 g of an olefin polymer. The Mw of the obtained olefin polymer was 106,000.

[0221] [Example 2] Polymerization was carried out in the same manner as in Example 1, except that the Group 13 element-containing compound (A-2) obtained in Production Example 4 was used instead of the Group 13 element-containing compound (A-1), to obtain 1.56 g of an olefin polymer. The Mw of the obtained olefin polymer was 214,000.

[0222] Comparative Example 2 Polymerization was carried out in the same manner as in Example 1, except that the Group 13 element-containing compound (A'-2) was used instead of the Group 13 element-containing compound (A-1), to obtain 1.04 g of an olefin polymer. The Mw of the obtained olefin polymer was 93,100.

[0223] [Example 3] Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B1-1) was used instead of transition metal complex (B2-1), and 0.200 μmol of Group 13 element-containing compound (A-1) (4 equivalents relative to the transition metal complex (B1-1)) was used, to obtain 0.87 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,170,000.

[0224] Comparative Example 3 Polymerization was carried out in the same manner as in Example 3, except that the Group 13 element-containing compound (A'-1) was used instead of the Group 13 element-containing compound (A-1), to obtain 0.43 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,270,000.

[0225] [Example 4] Polymerization was carried out in the same manner as in Example 1, except that 2.000 μmol of transition metal complex (B3-1) was used instead of transition metal complex (B2-1), and 8.000 μmol of Group 13 element-containing compound (A-1) (4 equivalents relative to the transition metal complex (B3-1)) was used, to obtain 0.011 g of olefin polymer.

[0226] Comparative Example 4 Polymerization was carried out in the same manner as in Example 4, except that the Group 13 element-containing compound (A'-1) was used instead of the Group 13 element-containing compound (A-1), to obtain 0.002 g of an olefin polymer.

[0227] [Example 5] Polymerization was carried out in the same manner as in Example 1, except that the Group 13 element-containing compound (A-5) obtained in Production Example 5 was used instead of the Group 13 element-containing compound (A-1), to obtain 1.58 g of an olefin polymer. The Mw of the obtained olefin polymer was 166,000.

[0228] Comparative Example 5 Polymerization was carried out in the same manner as in Example 1, except that the Group 13 element-containing compound (A'-5) obtained in Production Example 6 was used instead of the Group 13 element-containing compound (A-1), to obtain 1.34 g of an olefin polymer. The Mw of the obtained olefin polymer was 103,000.

[0229] [Example 6] Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B1-1) was used instead of transition metal complex (B2-1), and 0.200 μmol (4 equivalents relative to the transition metal complex (B1-1)) of Group 13 element-containing compound (A-2) obtained in Production Example 4 was used instead of Group 13 element-containing compound (A-1), to obtain 0.85 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,290,000.

[0230] Comparative Example 6 Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B1-1) was used instead of transition metal complex (B2-1), and 0.200 μmol of Group 13 element-containing compound (A'-2) (4 equivalents relative to the transition metal complex (B1-1)) was used instead of Group 13 element-containing compound (A-1), to obtain 0.59 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,450,000.

[0231] [Example 7] Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B1-1) was used instead of transition metal complex (B2-1), and 0.200 μmol (4 equivalents relative to the transition metal complex (B1-1)) of Group 13 element-containing compound (A-5) obtained in Production Example 5 was used instead of Group 13 element-containing compound (A-1), to obtain 1.16 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,450,000.

[0232] Comparative Example 7 Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B1-1) was used instead of transition metal complex (B2-1), and 0.200 μmol (4 equivalents relative to the transition metal complex (B1-1)) of Group 13 element-containing compound (A'-5) obtained in Production Example 6 was used instead of Group 13 element-containing compound (A-1), to obtain 0.46 g of an olefin polymer. The Mw of the obtained olefin polymer was 1,510,000.

[0233] [Example 8] Polymerization was carried out in the same manner as in Example 1, except that 0.015 μmol of transition metal complex (B2-2) was used instead of the transition metal complex (B2-1), and 0.060 μmol (4 equivalents relative to the transition metal complex (B2-2)) of the Group 13 element-containing compound (A-5) obtained in Production Example 5 was used instead of the Group 13 element-containing compound (A-1), to obtain 0.49 g of an olefin polymer.

[0234] [Comparative Example 8] Polymerization was carried out in the same manner as in Example 1, except that 0.050 μmol of transition metal complex (B2-2) was used instead of the transition metal complex (B2-1), and 0.200 μmol (4 equivalents relative to the transition metal complex (B2-2)) of the Group 13 element-containing compound (A'-5) obtained in Production Example 6 was used instead of the Group 13 element-containing compound (A-1), to obtain 0.04 g of an olefin polymer.

[0235] The evaluation results of Examples 1 to 8 and Comparative Examples 1 to 8 are shown in Table 1. In Table 1, "polymerization activity" indicates the yield (kg) of olefin polymer per 1 mmol of total transition metal atoms (M) in the transition metal complex (B) per unit time (hr).

[0236] [Table 1-1]

[0237] [Table 1-2]

[0238] <Pressure Solution Polymerization of Ethylene / 1-Octene Using Group 13 Element-Containing Compounds> [Example 9] A 1-L stainless steel autoclave with a thoroughly nitrogen-purged interior was charged with 470 mL of heptane, 30 mL of 1-octene, and 0.30 mmol of triisobutylaluminum under a nitrogen atmosphere. Ethylene was then passed through to saturate the reactor. Next, the temperature and pressure were raised to 80°C and 0.8 MPaG with ethylene while stirring. 0.050 μmol of the transition metal compound (B2-3) described above was added, followed by 0.50 μmol of the Group 13 element-containing compound (A-1) obtained in Production Example 1. Polymerization was carried out for 10 minutes, and the polymerization was terminated by the addition of a small amount of methanol. After polymerization, the reactants were added to 1 L of a 1 / 3 methanol / acetone mixed solvent containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the polymer was vacuum-dried at 80°C for 10 hours, yielding 4.23 g of olefin polymer. The 1-octene content of the resulting polymer was 17.8 mol%.

[0239] Comparative Example 9 Polymerization was carried out in the same manner as in Example 9, except that the Group 13 element-containing compound (A'-1) was used instead of the Group 13 element-containing compound (A-3), to obtain 3.64 g of an olefin polymer. The 1-octene content of the obtained polymer was 17.7 mol%.

[0240] The evaluation results of Example 9 and Comparative Example 9 are shown in Table 2. In Table 2, "polymerization activity" indicates the yield (kg) of olefin polymer per 1 mmol of total transition metal atoms (M=Hf) in the transition metal complex (B) per unit time (hr).

[0241] [Table 2]

[0242] The results in Tables 1 and 2 show that the olefin polymerization catalyst of the present invention, which uses the Group 13 element-containing compound (A) as a co-catalyst, produced more olefin polymers than the comparative examples, which used a commonly used borate co-catalyst having the same cation species and the same transition metal complex (B). This demonstrates that the olefin polymerization catalyst of the present invention, which uses the Group 13 element-containing compound (A) as a co-catalyst, exhibits high polymerization activity.

Claims

1. A Group 13 element-containing compound (A) represented by the following general formula (A), At least one transition metal complex (B) selected from the group consisting of a compound represented by the following general formula (B1), a compound represented by the following general formula (B2), a compound represented by the following general formula (B3), a compound represented by the following general formula (B4), a compound represented by the following general formula (B5), and a compound represented by the following general formula (B6). A catalyst for olefin polymerization comprising: [a] γ+ {b} γ- …(A) [In the general formula (A), γ is an integer of 1 to 5. [α] γ+ is a cation represented by the following general formula (α-1), (α-2) or (α-3). [(R 1 ) 3 NH] + …(α-1) [(R) 2 ) 3 C] + …(a-2) [(R) 3 ) 3 N-R 4 -N(R 3 ) 3 ] γ+ …(a-3) (In general formulas (α-1), (α-2) and (α-3), a plurality of R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a hydrocarbon group having 1 to 30 carbon atoms, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms, and may be bonded to each other to form a ring. 4 is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group containing a hetero atom, and R 4 and one or more R 3 may be bonded to each other to form a ring.) {β} γ- represents one or more anions (β), the total valence of said anions (β) being γ. The anion (β) is an anion (β-1) represented by the following general formula (β-1) or an anion (β-2) other than the above (β-1). [MQM 4 ] - …(b-1) (In general formula (β-1), M is an atom of a Group 13 element. The four Qs are independently an aryl group, and at least one of the four Qs is an aryl group (Q-0) having one or more halogen atoms selected from a chlorine atom, a bromine atom, and an iodine atom as a substituent. At least one of the anions (β) is the anion (β-1). When a plurality of anions (β) are present, they may be the same or different. 【Chemical 1】 (In general formulas (B1) to (B3), M represents an atom of Group 4 or 5 of the periodic table; Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair; j represents an integer of 1 to 4, Cp 1 and Cp 2 may be the same or different and represent a cyclopentadienyl group or a substituted cyclopentadienyl group capable of forming a sandwich structure together with M; In general formula (B2), Y represents a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO 2 —, —Ge—, —Sn—, —NR a —, —P(R a )—, —P(O)(R a )—, —BR a —, or —AlR a —; R a represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, or a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a nitrogen atom (-NRH or -NR 2 ; R is a hydrocarbon group having 1 to 20 carbon atoms). 【Chemistry 2】 (In the general formula (B4), M represents a transition metal atom of Groups 4 to 10 of the periodic table, m represents an integer of 1 to 6, R 19 to R 24 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring; When m is 2 or more, two of the groups represented by R 19 to R 24 may be linked together; n is a number that satisfies the valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other to form a ring. 【Chemistry 3】 (In general formula (B5), R 25 to R 30 may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other, and R 25 may be linked to Z; M represents a transition metal atom selected from Groups 3 to 10 of the periodic table; n represents the valence of M; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be the same or different from each other and may be bonded to each other to form a ring; Y represents an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom; Z represents a hydrocarbon group which may have a substituent; The dotted lines indicate coordinate bonds.) L 1 M 1 X n...(B6) (In the general formula (B6), M 1 is a metal of Group 4 or the lanthanide series of the periodic table, L 1 is a derivative of a delocalized π-bonded group; X's each independently represent hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group, or a germyl group; n is an integer of 1 to 2.

2. 2. The olefin polymerization catalyst according to claim 1, wherein, in the general formula (A), at least one of the aryl groups (Q-0) is an aryl group represented by the following general formula (Q-1): 【Chemistry 4】 In the general formula (Q-1), * represents a bond to the M, and a plurality of X a are independently halogen atoms selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a plurality of X a At least one of the groups is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

3. In the general formula (Q-1), two X's located at meta positions with respect to the bond to M a 3. The olefin polymerization catalyst according to claim 2, wherein at least one of the following is a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

4. The olefin polymerization catalyst according to claim 3, wherein the aryl group represented by the general formula (Q-1) is an aryl group represented by the following general formula (Q-1a) or (Q-1b): 【Chemistry 5】 In the general formulae (Q-1a) and (Q-1b), * represents a bond to the M, and a plurality of X m are independently a halogen atom selected from a chlorine atom, a bromine atom, and an iodine atom.

5. 2. The olefin polymerization catalyst according to claim 1, wherein in said general formula (A), M is a boron atom.

6. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5.

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