Group 13 element-containing compound, olefin polymerization catalyst, and method for producing olefin polymer

Abstract

To provide: a novel group 13 element-containing compound useful as a co-catalyst in an olefin polymerization catalyst and capable of exhibiting high olefin polymerization activity; and an olefin polymerization catalyst and the like using the same.SOLUTION: The invention provides a group 13 element-containing compound (A) represented by the following general formula (A). [R1R2R3 NH]+[MQ4]- (A). (In the formula (A), M is a group 13 element atom, four Q's are each independently an aryl group and at least one of R1, R2 and R3 is a substituent represented by the general formula (I). (In the general formula (I), the symbol * is a bond to a nitrogen atom, and a plurality of Ra's are each independently a hydrocarbon group, a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a heteroatom-containing hydrocarbon group, or a group in which some or all of carbon atoms of the hydrocarbon group and the heteroatom-containing hydrocarbon group are replaced with silicon atoms or germanium atoms.))SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a Group 13 element-containing compound, more particularly to a Group 13 element-containing compound useful as a cocatalyst in an olefin polymerization catalyst, as well as an olefin polymerization catalyst and a method for producing an olefin polymer using the same. [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. 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. In particular, tertiary ammonium ions having one hydrogen atom and three alkyl (aliphatic) or aryl (aromatic) groups as substituents on the nitrogen atom are widely used as cations. Among these, tertiary ammonium ions having at least one aryl group as a substituent are superior in terms of olefin polymerization activity, and therefore many techniques relating to borate compounds of tertiary ammonium ions having an aryl group as a substituent on the nitrogen atom have been reported (e.g., Patent Documents 1 to 3).

[0003] On the other hand, it has been disclosed that tertiary trialkylammonium ions that do not have an aryl group as a substituent on the nitrogen atom have excellent affinity with aliphatic hydrocarbon solvents (for example, Patent Document 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 5-502906 [Patent Document 2] Special Publication No. 2021-522243 [Patent Document 3] International Publication No. 2019 / 210030 [Patent Document 4] Special Publication No. 2000-507157 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional borate compounds of tertiary trialkylammonium ions have room for further improvement in terms of olefin polymerization activity. Therefore, an object of the present invention is to provide a novel Group 13 element-containing compound that is useful as a cocatalyst in an olefin polymerization catalyst and is also capable of exhibiting high polymerization activity in olefin polymerization, as well as an olefin polymerization catalyst and a method for producing an olefin polymer using the same. [Means for solving the problem]

[0006] The present invention relates to, for example, the following [1] to [5]. [1] A compound (A) containing a Group 13 element represented by the following general formula (A): [R 1 R 2 R 3 NH] + [MQ4] - …(A) (In the general formula (A), R 1 , R 2 and R 3 each independently represents a hydrocarbon group having from 1 to 30 carbon atoms, a hydroxy group, an amino group, a sulfanyl group, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or the heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms, and may be bonded to each other to form a ring, R 1 , R 2 and R 3 At least one of the groups is a substituent represented by the following general formula (I). M is an atom of a Group 13 element. Each of the four Qs is independently an aryl group.

[0007] [ka] (In the above general formula (I), * is a bond to a nitrogen atom. Multiple R's a are each independently a hydrocarbon group, a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or the heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms, and may be bonded to each other to form a ring.

[0008] [2] The Group 13 element-containing compound (A) according to [1], wherein in the general formula (A), M is a boron atom.

[0009] [3] [1] A catalyst for olefin polymerization, comprising the Group 13 element-containing compound (A) according to the present invention, a transition metal complex (B), and at least one compound (C) selected from the group consisting of organometallic compounds (C-1) and organoaluminum oxy compounds (C-2).

[0010] [4] The olefin polymerization catalyst according to [3], further comprising a porous material (S).

[0011] [5] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to [3] or [4]. [Effects of the Invention]

[0012] According to the present invention, there are provided a novel Group 13 element-containing compound which is useful as a cocatalyst in an olefin polymerization catalyst and which is also capable of exhibiting high polymerization activity in olefin polymerization, as well as an olefin polymerization catalyst and a method for producing an olefin polymer using the same. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will now be described in further detail. [Group 13 element-containing compound (A)] The Group 13 element-containing compound (A) according to the present invention (hereinafter also referred to simply as "compound (A)" or "component (A)") is characterized by being represented by the following general formula (A): [R 1 R 2 R 3 NH] + [MQ4] - …(A) ([R 1 R 2 R 3 NH] + The cation moiety represented by <R 1 , R 2 and R 3 > In general formula (A), R 1 , R 2 and R 3 are each independently a hydrocarbon group having from 1 to 30 carbon atoms, a hydroxy group, an amino group, a sulfanyl group, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the above hydrocarbon group and the above heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms, and may be bonded to each other to form a ring.

[0014] Furthermore, R 1 , R 2 and R 3 At least one of the groups is a substituent represented by the following general formula (I).

[0015] [ka] (In general formula (I), * is a bond to a nitrogen atom. Multiple R's aare each independently a hydrocarbon group, a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, a heteroatom-containing hydrocarbon group, or a group in which some or all of the carbon atoms of the hydrocarbon group or the heteroatom-containing hydrocarbon group have been replaced with silicon atoms or germanium atoms. Multiple R's a may be bonded to each other to form a ring. [R 1 R 2 R 3 NH] + In the formula (I), the number of the substituents is preferably 1 to 2.

[0016] When a hydroxy group is present at the position shown in general formula (I), it is presumed that when olefin polymerization is carried out in the presence of a catalyst containing compound (A) and a transition metal complex (B) described below, the hydroxy group reacts or interacts with an organoaluminum compound in the polymerization solution, thereby acting as an electron-withdrawing group and improving the acid strength of the cation, thereby contributing to the activation of the transition metal complex (B), resulting in high polymerization activity. In general formula (I), four R a Two R bonds to the carbon atom that has a hydroxy group bonded to it. a are hydrogen atoms (in other words, the hydroxyl group is attached to the terminal carbon atom of the carbon chain), a When olefin polymerization is carried out in the presence of a catalyst containing compound (A), a transition metal complex (B) described later, and compound (C) (preferably, an organoaluminum compound (C-1)), a high polymerization activity is exhibited compared to when only one of the compounds is a hydrogen atom.

[0017] In addition, R other than the substituents represented by the general formula (I) 1 , R 2 and R 3is preferably 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 the heteroatom-containing hydrocarbon group have been substituted with silicon atoms or germanium atoms, more preferably a hydrocarbon group having 1 to 30 carbon atoms or a heteroatom-containing hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 30 carbon atoms.

[0018] Hereinafter, in the general formula (A), R 1 , R 2 and R 3 The substituents that can be mentioned as the following will be described in detail. hydrocarbon group The hydrocarbon group has 1 or more and 30 or less carbon atoms, preferably 1 or more and 18 or less carbon atoms. 1 , R 2 and R 3 When is a hydrocarbon group having such a carbon number, compound (A) has excellent affinity for hydrocarbon solvents.

[0019] 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.

[0020] 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-nonadecyl, 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-methylpentyl linear or branched alkyl groups having 1 to 30 carbon atoms, such as hexyl, 2-methylpentan-2-yl, 4-methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, 3,3-dimethylbut-2-yl, hexane-3-yl, 2-methylpentan-3-yl, heptan-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, and 2,4,4-trimethylpentan-2-yl (tert-octyl); 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.

[0021] 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 heptan-4-yl group, a 2,4- Dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl group (tert-octyl group), and the like are preferred, and hydrocarbon groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, n-octadecyl group, isopropyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentan-2-yl group, 2,4,4-trimethylpentan-2-yl group (tert-octyl group) are more preferred.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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, and a 3-n-hexylphenyl group are , 3-n-heptylphenyl 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 group, 3,5-di-n-octadecylphenyl group, 3,5-di(2,4,4-trimethylpentan-2-yl)phenyl group, 3,5-diadamantylphenyl group, mesityl group, cumenyl group, 2,6-di-isopropylphenyl group, 2,4,6-tri-isopropylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthyl group, Tolyl, anthracenyl, ferrocenyl, and the like are preferred, and phenyl, tolyl, xylyl, mesityl, cumenyl, 2,6-di-isopropylphenyl, 2,4,6-tri-isopropylphenyl, allylphenyl, naphthyl, biphenyl, phenanthryl, anthracenyl, 4-n-octylphenyl, and 4-(2,4,4-trimethylpentan-2-yl)phenyl are more preferred.

[0027] halogen atoms In the general formula (I), examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Preferably, it is fluorine or chlorine.

[0028] Heteroatom-containing hydrocarbon groups An example of the heteroatom-containing hydrocarbon group in general formula (A) and general formula (I) is one in which some or all of the hydrogen atoms in the hydrocarbon group are replaced with halogen atoms or heteroatom-containing groups. For example, in general formula (A), one in which some of the hydrogen atoms in the hydrocarbon group having 1 to 30 carbon atoms are replaced with hydroxy groups is included. That is, the substituent represented by general formula (I) is a group represented by R 1 , R 2 , and R 3 In this case, when a plurality of R a Examples of the hydrocarbon group as the substituent include the same as those given as specific examples of the hydrocarbon group having 1 to 30 carbon atoms in the general formula (A) above (however, the total number of carbon atoms in the substituent represented by the general formula (I) is selected within a range of 30 or less). 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)- (R is a hydrogen atom or a hydrocarbon group, and the number of carbon atoms is selected so that the total number of carbon atoms in the substituents represented by general formula (I) is 30 or less), -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.

[0029] 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 hydrocarbon groups in which some or all of the hydrogen atoms have been replaced with halogen atoms (hereinafter also referred to as "halogen atom-containing hydrocarbon groups") 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 the halogen atom-containing hydrocarbon groups, a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group, and a pentafluorobenzyl group are more preferred.

[0032] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy 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 octadecyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an isopropylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an isopropoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxy Examples of such groups include an ethyl 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 dodecyloxy group and an octadecyloxy 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 aminopropyl group, phenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-isopropyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyljulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, isoquinolyl group, tetrahydro-isoquinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, Zo Examples of the alkyl group include an aryl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

[0035] Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolyl group, a pyridyl group, an indolyl group, an indolinyl group, a carbazolyl group, a benzimida group, Zo An aryl group, a benzoxazolyl group, and the like are 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 in general formula (A) and general formula (I) include the above-mentioned hydrocarbon groups in which some or all of the hydrogen atoms have been replaced with halogen atoms or heteroatom-containing groups, and further include groups in which some of the methylene groups have been replaced with a structure represented by -CO-, -CH(OH)-, -NR-, -PR-, -P(O)(R)- (R is a hydrogen atom or a hydrocarbon group, and the number of carbon atoms is selected so that the total number of carbon atoms in the substituents represented by general formula (I) is 30 or less), -O-, -S-, or -SO2-, and groups in which some of the methine groups in the hydrocarbon groups have been replaced with a nitrogen atom, a phosphorus atom, or a structure represented by ≡SiH.

[0041] A group in which some or all of the carbon atoms of the hydrocarbon group and the heteroatom-containing hydrocarbon group are replaced with silicon atoms or germanium atoms. Examples of the substituent in the general formula (A) and the general formula (I) include a trihydrosilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylhydrosilyl 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 fluorenyl butyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris(trimethylsilyl)silylphenyl group, 3,5-bis(trimethylsilyl)phenyl group, trifluorosilyl group, trichlorosilyl group, N,N-bis(trimethylsilyl)amino group, trimethylgermyl group, triethylgermyl group, tert-butyldimethylgermyl group, 4-trimethylgermylphenyl group, 4-triethylgermylphenyl group, 4-tri-iso-propylgermylphenyl group, and 3,5-bis(trimethylgermyl)phenyl group.

[0042] Among the 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, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, and a trifluorosilyl group are more preferred.

[0043] Also, R 1 ,R 2 ,R 3 and / or R aTwo or more of these groups may be bonded to each other to form a ring, or may not be bonded to each other. From the viewpoint of ease of production, etc., it is preferable that these groups are not bonded to each other.

[0044] <Examples of cations> [R 1 R 2 R 3 NH] + Specific examples of the cation represented by the formula include cations represented by the formula below.

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] ([MQ4] - The anion portion represented by In general formula (A), M is an atom of a Group 13 element, and the four Qs are each independently an aryl group. The aryl group may or may not have a substituent. A plurality of Qs may be bonded to each other to form a ring, or may not be bonded to each other.

[0049] The 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.

[0050] The aryl group represented by Q (hereinafter also referred to as "aryl group (Q)") is preferably an aryl group having 6 to 20 carbon atoms (hereinafter also referred to as "aryl group (Q1)") represented by the following general formula (Q1):

[0051] [ka] (In general formula (Q1), * represents a bond to an atom of a Group 13 element. The multiple Rs are each independently a substituent (rq1) selected from the group consisting of halogen atoms, hydrocarbon groups, heteroatom-containing hydrocarbon groups, and groups in which some of the carbon atoms of the hydrocarbon groups and heteroatom-containing hydrocarbon groups have been substituted with silicon atoms or germanium atoms, or a hydrogen atom, and at least one of the Rs adjacent to * (i.e., the R in the ortho position relative to the bond to the atom of the Group 13 element) is the substituent (rq1). When a plurality of the substituents (rq1) are present, the plurality of substituents (rq1) may be the same as or different from one another. The plurality of substituents (rq1) may be bonded to one another to form an aromatic ring which may have a substituent, or may not be bonded to one another.

[0052] Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0053] 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. The hydrocarbon group may or may not have an unsaturated bond, and the aliphatic hydrocarbon group may be linear or branched.

[0054] Specific examples of the hydrocarbon group include: R in the general formula (I) aExamples of the substituent include the linear or branched alkyl groups listed as specific examples of the above; linear or branched alkenyl groups or unsaturated double bond-containing groups; linear or branched alkynyl groups or unsaturated triple bond-containing groups; aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups; cyclic saturated and unsaturated hydrocarbon groups; and aromatic hydrocarbon groups. When the phenyl group has one substituent, the position of the substituent is the ortho-, meta-, or para-position, preferably the para-position.

[0055] Among the linear or branched alkyl groups, the R a The hydrocarbon groups having 1 to 30 carbon atoms mentioned as preferred groups are more preferred.

[0056] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups, the R a The groups given as preferred groups are more preferred.

[0057] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups, the R a The groups given as preferred groups are more preferred.

[0058] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups, preferred embodiments are those in which the R a This is the same as the preferred embodiment of the above.

[0059] Among the above-mentioned cyclic saturated and unsaturated hydrocarbon groups, preferred embodiments are those in which the R a This is the same as the preferred embodiment of the above.

[0060] Among the aromatic hydrocarbon groups, preferred embodiments are those in which the R a This is the same as the preferred embodiment of the above.

[0061] Examples of heteroatom-containing hydrocarbon groups include: A part or all of the hydrogen atoms in the hydrocarbon group represented by R may be replaced by R athose substituted with heteroatom-containing groups mentioned in the description of Examples of such hydrocarbon groups represented by R include groups in which some of the methylene groups have been replaced with a structure represented by -CO-, -CH(OH)-, -NR'-, -PR'-, -P(O)(R')- (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 have been replaced with a nitrogen atom, a phosphorus atom, or a structure represented by ≡SiH (with the proviso that the number of carbon atoms in the aryl group represented by general formula (Q1) is selected within a range of 30 or less), and preferred are halogen-containing hydrocarbon groups. The halogen atoms in such halogen-containing hydrocarbon groups are preferably fluorine atoms. A proton may be coordinately bonded to some or all of the heteroatoms (preferably nitrogen atoms) contained in the heteroatom-containing hydrocarbon group.

[0062] The halogen atom-containing hydrocarbon group preferably includes 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, and a pentafluorophenyl group, and among these, perfluorohydrocarbon groups such as a trifluoromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group are preferred.

[0063] Preferred examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group in which some of the carbon atoms have been substituted with silicon atoms or germanium atoms include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group. The R is preferably a halogen atom or a heteroatom-containing hydrocarbon group, and particularly preferably a fluorine atom, a trifluoromethyl group, or a perfluorophenyl group (pentafluorophenyl group).

[0064] The substituent (rq1) at at least one ortho-position of the aryl group (ortho-position relative to the bond to the atom of the Group 13 element) is preferably an electron-withdrawing group, more preferably a halogen atom or a halogen-containing hydrocarbon group, and even more preferably a halogen atom. When the compound (A) of the present invention has an electron-withdrawing group at the ortho-position, it exhibits excellent performance as a co-catalyst in an olefin polymerization catalyst.

[0065] Examples of aromatic rings formed by bonding multiple substituents (rq1) together include naphthalene, anthracene, and phenanthrene. This aromatic ring may have a substituent, and this substituent is preferably a halogen atom or a halogenated alkyl group, more preferably a fluorine atom or a trifluoromethyl group.

[0066] [MQ4] - Specific examples of the anion, in which each Q is independently the aryl group (Q1), include a tetrakis(2,4-dimethylphenyl)borate ion, a tetrakis(2,4,6-trifluorophenyl)borate ion, a tris(pentafluorophenyl)(1-naphthyl)borate ion, and a tetrakis(pentafluorophenyl)borate ion (hereinafter referred to as "[B(CF)] -"), tetrakis(3,5-bis(trimethylsilyl)trifluorophenyl)borate ion, tetrakis(3,5-bis(triisopropylsilyl)trifluorophenyl)borate ion, tetrakis(3,5-bis(tert-butyldimethylsilyl)trifluorophenyl)borate ion, tetrakis(3,5-bis(trifluoromethyl)trifluorophenyl)borate ion, tetrakis(perfluorobiphenyl-2-yl)borate ion, (pentafluorophenyl)tris(perfluorobiphenyl-2-yl)borate ion, ion, bis(pentafluorophenyl)bis(perfluorobiphenyl-2-yl)borate ion, tris(pentafluorophenyl)(perfluorobiphenyl-2-yl)borate ion, tetrakis(perfluorobiphenyl-3-yl)borate ion, (pentafluorophenyl)tris(perfluorobiphenyl-3-yl)borate ion, bis(pentafluorophenyl)bis(perfluorobiphenyl-3-yl)borate ion, tris(pentafluorophenyl)(perfluorobiphenyl-3-yl)borate ion ion, tetrakis(α-perfluoronaphthyl)borate ion, (pentafluorophenyl)tris(α-perfluoronaphthyl)borate ion, bis(pentafluorophenyl)bis(α-perfluoronaphthyl)borate ion, tris(pentafluorophenyl)(α-perfluoronaphthyl)borate ion, tetrakis(β-perfluoronaphthyl)borate ion, (pentafluorophenyl)tris(β-perfluoronaphthyl)borate ion, bis(pentafluorophenyl)bis(β-perfluoronaphthyl)borate ion, tris(pentafluorophenyl)(β-perfluoronaphthyl)borate ion, bis(3,4,5,6,3',4',5',6'-octafluorobiphenyl-2,2'-diyl)borate ion, anions in which the fluorine atom in these anions is replaced with another halogen atom such as a chlorine atom or a bromine atom, and anions in which the boron atom in these anions is replaced with another Group 13 element described above (for example, tetrakis(pentafluorophenyl)aluminate ion, tetrakis(α-perfluoronaphthyl)aluminate ion, etc.).

[0067] Among these, [B(C6F5)4] - , tetrakis(3,5-bis(trifluoromethyl)trifluorophenyl)borate ion, tetrakis(perfluorobiphenyl-3-yl)borate ion, tris(pentafluorophenyl)(perfluorobiphenyl-3-yl)borate ion, tetrakis(2-perfluorobiphenyl)borate ion, tetrakis(α-perfluoronaphthyl)borate ion, tetrakis(β-perfluoronaphthyl)borate ion, and bis(3,4,5,6,3',4',5',6'-octafluorobiphenyl-2,2'-diyl)borate ion are preferred, and [B(CF)] - , tetrakis(α-perfluoronaphthyl)borate ion, tetrakis(β-perfluoronaphthyl)borate ion, tetrakis(pentafluorophenyl)aluminate ion, and tetrakis(α-perfluoronaphthyl)aluminate ion are particularly preferred.

[0068] The aryl group (Q) also includes aryl groups other than the aryl group (Q1) (hereinafter also referred to as "aryl group (Q2)"). Preferred examples of the aryl group (Q2) include a phenyl group, an m-tolyl group, a p-tolyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2-naphthyl group, a 3-biphenyl group, a 4-biphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 3,5-bis(trifluoromethyl)-4-fluorophenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-(4'-hydroxyphenyl)phenyl group, a 6-hydroxy-2-naphthyl group, a 4-aminophenyl group, a 4-hydroxy-2,3,5,6-tetrafluorophenyl group, and a 4-amino-2,3,5,6-tetrafluorophenyl group.

[0069] [MQ4] -Specific examples of the anion having at least one aryl group (Q2) as Q include a tetrakisphenylborate ion, a tetrakis(p-tolyl)borate ion, a tris(p-tolyl)(phenyl)borate ion, a tris(pentafluorophenyl)(phenyl)borate ion, a tris(2,4-dimethylphenyl)(phenyl)borate ion, a tetrakis(3,5-dimethylphenyl)borate ion, a tris(3,5-dimethylphenyl)(phenyl)borate ion, a tetrakis(3,5-bis(trifluoromethyl) phenyl)borate ion, tris(3,5-bis(trifluoromethyl)phenyl)(phenyl)borate ion, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ion, tetrakis(3,5-bis(trifluoromethyl)-4-fluorophenyl)borate ion, triphenyl(3-hydroxyphenyl)borate ion, triphenyl(4-hydroxyphenyl)borate ion, diphenyl-di(4-hydroxyphenyl)borate ion, triphenyl(3,4-dihydroxyphenyl)borate ion, tri( p-tolyl)(4-hydroxyphenyl)borate ion, tris(pentafluorophenyl)(4-hydroxyphenyl)borate ion, tris(2,4-dimethylphenyl)(4-hydroxyphenyl)borate ion, tris(3,5-dimethylphenyl)(4-hydroxyphenyl)borate ion, tris(3,5-bis(trifluoromethyl)phenyl)(4-hydroxyphenyl)borate ion, tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate ion, tris(pentafluorophenyl) tris(pentafluorophenyl)(4-hydroxyphenyl)borate ion, tetrakis(3,5-bis(trifluoromethyl)-4-fluorophenyl)borate ion, triphenyl(4-aminophenyl)borate ion, diphenyl-di(4-aminophenyl)borate ion, tris(pentafluorophenyl)(4-aminophenyl)borate ion, tetra(4-hydroxy-2,3,5,6-tetrafluorophenyl)borate ion, tetra(4-amino-2,3,5,6-tetrafluorophenyl)borate ions, those in which the fluorine atom in these borate ions is replaced with another halogen atom such as a chlorine atom or a bromine atom, and those in which the boron atom in these anions is replaced with another Group 13 element as described above.

[0070] Among these, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ion and tetrakis(bis(3,5-bis(trifluoromethyl)-4-fluorophenyl)borate ion are preferred.

[0071] <Specific Examples of Group 13 Element-Containing Compound (A)> Specific examples of the Group 13 element-containing compound (A) of the present invention include compounds represented by the following formulae (A-1) to (A-9) and (A-21) to (A-23).

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] <Method for producing Group 13 element-containing compound (A)> Examples of the method for producing the Group 13 element-containing compound (A) according to the present invention include methods using the methods described in U.S. Patent Application Publication No. 2019 / 0330392, U.S. Patent No. 5,493,056, U.S. Patent No. 7,297,653, and U.S. Patent No. 11,041,031. Specifically, compound (A) can be produced mainly by a two-step method as follows.

[0076] The first step is to prepare a compound represented by general formula (A'):R 1 R 2R 3 N (wherein, R 1 , R 2 and R 3 are R in the general formula (A), respectively. 1 , R 2 and R 3 is synonymous with the general formula (A″): [R 1 R 2 R 3 NH] + Cl - (In the formula, R 1 , R 2 and R 3 are R in the general formula (A), respectively. 1 , R 2 and R 3 The salt (A'') is synthesized. The resulting salt (A'') is isolated by filtration or the like.

[0077] In the second step, the salt (A'') and the compound of the general formula [MQ4] - and an alkali metal salt (lithium borate salt, lithium aluminate salt, sodium borate salt, sodium aluminate salt, etc.) containing an anion represented by the formula (I) in a solvent (cyclohexane, dichloromethane, methylcyclohexane, etc.), compound (A) and an alkali metal chloride by-product can be synthesized, and compound (A) can be isolated by removing the latter by filtration or the like.

[0078] [Olefin polymerization catalyst] The olefin polymerization catalyst of the present invention contains the above-mentioned compound (A) of the present invention, transition metal complex (B), and compound (C).

[0079] <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. Examples of the transition metal complex (B) include 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).

[0080] [ka]

[0081] In the 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.

[0082] In formulas (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.

[0083] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] In 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.

[0093] In 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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).

[0098] 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.

[0099] 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.

[0100] 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 bond of the unsaturated ring fused to the cyclopentadienyl group may be hydrogenated.

[0101] In formulas (B2) and (B3), 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 (tin)-, 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).

[0102] In the formula (B3), X represents a hydrocarbon group having 1 to 6 carbon atoms.

[0103] 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.

[0104] [ka]

[0105] 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.

[0106] The cyclopentadienyl group, fluorenyl group, crosslinking portion and other features of the bridged metallocene compound (B2a) will be explained below in order. (cyclopentadienyl group) In 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] (fluorenyl group) In 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 11 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; R7 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.

[0111] 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.

[0112] 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 12 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. 5 ~R 12Examples of the heteroatom-containing group in include the groups exemplified above for the substituted cyclopentadienyl group.

[0113] R 6 and R 7 (R 10 and R 11 ) are bonded to each other to form an alicyclic or aromatic ring, the substituted fluorenyl group preferably includes groups having structures derived from compounds represented by the general formulae [I] to [VI] described later.

[0114] (Bridge part) In 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.

[0115] 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.

[0116] 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.

[0117] (Other features of bridged metallocene compounds) In 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.

[0118] 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.

[0119] (Examples of preferred bridged metallocene compounds (B2a)) 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], tetramethyldodecahydrodibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [II], octamethyltetrahydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [III], dibenzofluorenyl refers to a group derived from a compound having a structure represented by formula [IV], 1,1',3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [V], and 1,3,3',6,6',8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a group derived from a compound having a structure represented by formula [VI].

[0120] [ka]

[0121] Specific examples of the metallocene compounds represented by general formula (B1), (B2), or (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. A preferred example of the bridged metallocene compound (B2) is a compound (B2b) represented by the following general formula (B2b).

[0122] [ka]

[0123] <R 1 From R 16 〉 In formula (B2b), R 1 , R 2 , R 3 , R 4 , 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.

[0124] R 1 From R 16 The hydrocarbon group, heteroatom-containing hydrocarbon group, and silicon-containing group in the formula (B2a) include R 1 ~R 14 Examples of the hydrocarbon groups, heteroatom-containing hydrocarbon groups, and silicon-containing groups are those exemplified as above.

[0125] R 1 From 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 R 16 ) may be bonded to each other to form a ring, and R 4and 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.

[0126] 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.

[0127] 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.

[0128] 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. 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.

[0129] [ka]

[0130] In this case, the transition metal complex (B) includes all enantiomers of the transition metal complex represented by general formula (B2b'), for example, the transition metal complex represented by general formula (B2b''), within the scope of the present invention.

[0131] [ka]

[0132] In the notation of formulas (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.

[0133] 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 compound of a specific structure and its enantiomer.

[0134] 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 , 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 , 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.

[0135] 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.

[0136] 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.

[0137] 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 1,2,3,4,7,8,9,10-dodecahydro-12H-dibenzo[b,h]fluorenyl group (a tetramethyldodecahydrodibenzofluorenyl group represented by the formula [II]), 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 [II]).

[0138] <M, Q, j> In formula (B2b), M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

[0139] 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 formula (B2a).

[0140] 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.

[0141] The metallocene compound represented by the general formula (B3) includes a half metallocene compound represented by the following formula (B-3). [ka]

[0142] 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.

[0143] [ka]

[0144] 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.

[0145] 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.

[0146] 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.

[0147] [ka]

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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).

[0152] 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)

[0153] 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.

[0154] 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.

[0155] [ka]

[0156] In 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.

[0157] 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]dimethyltitanium], and compounds in which titanium in these compounds is replaced with zirconium or hafnium, and compounds in which 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)), etc. are included. The transition metal complex (B) may be used alone or in combination of two or more.

[0158] (Compound (C)) The olefin polymerization catalyst of the present invention 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 represent hydrocarbon groups 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 where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3. ]

[0159] [[ID=,37]]M a AlR a 4… (C-1b) [In the general formula (C-1b), M a represents Li, Na or K, and R[[ID=,46]] arepresents a hydrocarbon group having 1 to 15 carbon atoms (preferably 1 to 4 carbon atoms).

[0160] 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)").

[0161] 《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.

[0162] 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.

[0163] 《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.

[0164] (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon solvent 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.

[0165] (2) A method in which water, ice or water vapor is directly reacted with an organoaluminum compound such as trialkylaluminum in a solvent such as benzene, toluene, diethyl ether or tetrahydrofuran.

[0166] (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 solvent such as decane, benzene, or toluene.

[0167] (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.

[0168] 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.

[0169] 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.

[0170] 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 under the names MMAO and TMAO.

[0171] 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.

[0172] 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.

[0173] <Porous material (S)> The olefin polymerization catalyst of the present invention may further contain a porous material (S). The porous material is a granular or particulate inorganic or organic compound. Examples of inorganic compounds include oxides such as SiO2, Al2O3, MgO, ZrO2, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these. Examples include natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Among these, porous oxides containing SiO2 and / or Al2O3 as the primary components are preferred. Additionally, inorganic chlorides, clay minerals or ion-exchangeable layered compounds may also be used.

[0174] Alternatively, the porous material [S] may be, for example, boron nitride, which satisfies the requirement that the molar ratio of oxygen atoms / (boron atoms + aluminum atoms + silicon atoms) measured by X-ray photoelectron spectroscopy (XPS) is 0.050 or more and less than 2.0. The oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio is a value obtained by X-ray photoelectron spectroscopy (XPS). Specifically, the oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio is calculated from the peak areas of oxygen atoms, boron atoms, aluminum atoms, and silicon atoms in a spectrum obtained from a component selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride. A higher oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio increases the amount of oxygen atoms available for contact with the organoaluminum oxy-compound, which is favorable in terms of olefin polymerization activity. On the other hand, an excessively high oxygen atom / (boron atom + aluminum atom + silicon atom) molar ratio increases the amount of organoaluminum oxy-compound required, which is undesirable in terms of catalyst cost. The boron nitride may be produced by a method such as that exemplified in JP 2021-91604 A, and boron nitride nanotubes produced by a method such as that exemplified in JP 2021-147309 A may also be used. Examples of commercially available products include "Boron nitride nanopowder, <150 nm avg. part size (BET), 99% trace metals basis" and "Boron nitride nanotubes Multiwalled, powder, >90%" from Sigma-Aldrich.

[0175] Alternatively, a carbon material may be used as the porous material [S]. The carbon material has an oxygen atom / carbon atom molar ratio of 0.018 to 0.400 as determined by X-ray photoelectron spectroscopy (XPS) and a specific surface area of ​​100 m2 as determined by the BET multipoint method. 2 / g or more 5000m 2 / g or less, preferably 150m 2 / g or more 3000m 2 / g or less.

[0176] The oxygen atom / carbon atom molar ratio is a value obtained by X-ray photoelectron spectroscopy (XPS) measurement, and specifically, the oxygen atom / carbon atom molar ratio is calculated from the peak areas of oxygen atoms and carbon atoms in the spectrum obtained from the carbon material. A higher oxygen atom / carbon atom molar ratio is preferable because it increases the number of oxygen atoms that can come into contact with the organoaluminum compound. However, if the oxygen atom / carbon atom molar ratio is too high, the sp 2 The two-dimensional sheet structure due to the bonded carbon tends to decrease. The carbon material is efficiently dispersed in the olefin polymer, and is expected to have high thermal conductivity, electrical conductivity, and weather resistance.

[0177] The carbon material is a solid carbon material and is not particularly limited as long as it satisfies the above requirements, and includes crystalline, low-crystalline, amorphous carbon materials and carbon materials consisting of mixtures thereof. Among the carbon materials, examples of crystalline carbon include carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), and multi-walled carbon nanotubes (MWCNT)), graphene (e.g., single-layered graphene, multi-layered graphene), fullerenes (e.g., buckminsterfullerene, higher fullerenes), graphite (e.g., natural graphite, artificial graphite), diamond, etc. Examples of low-crystalline and amorphous carbon include carbon black, activated carbon, etc.

[0178] Carbon nanotubes can be produced by methods such as arc discharge, laser deposition, and gas-phase chemical vapor deposition, as exemplified in JP 2009-196873 A, and can be surface-modified by methods such as those exemplified in JP 2014-501689 A. Commercially available products include "Multi-Walled Carbon Nanotubes NANOCYL NC7000" and "Multi-Walled Carbon Nanotubes NANOCYL NC3101" from Nanocyl Corporation, "Single-Walled Nanotubes OH Functionalized" and "Multi-Walled Nanotubes OH Functionalized" from SkySpring Nanomaterials, and "Multi-Walled Carbon Nanotubes, -OH Functionalized" from IoLiTec.

[0179] Graphene can be produced by methods such as arc discharge, laser deposition, vapor-phase chemical vapor deposition, heat treatment of silicon carbide, mechanical exfoliation, and ultrasonic exfoliation after chemical oxidation, as exemplified in JP 2014-152095 A. Commercially available graphene products include "Graphene Nanoplatelets xGnP" from XG Sciences, and "Reduced Graphene Oxide," "Boron-doped Graphene Powder," "Phosphorus-doped Graphene Powder," "Sulfur-doped Graphene Powder," "Nitrogen-doped Graphene Powder," and "Graphene Film" from Graphitene.

[0180] Fullerenes are produced by methods such as arc discharge, resistance heating, laser evaporation, combustion, and pyrolysis, as exemplified in JP 2013-241379 A, ​​and hydroxyl groups and carboxyl groups can be introduced onto the carbon of fullerenes by chemical treatment. Commercially available fullerenes include "C 60 PCPA" "C 60 (OH) 22-26 " and others.

[0181] Graphite can be broadly divided into natural graphite and artificial graphite, and examples of natural graphite include flake graphite, lump graphite (flake graphite), and amorphous graphite. Artificial graphite can be produced by methods such as precipitation from an Fe, Ni / C melt, decomposition of carbides of Si, Al, etc., cooling of a carbon melt under high temperature and pressure, and high-temperature decomposition and deposition of hydrocarbon gas, as exemplified in Japanese Patent Laid-Open Publication No. 02-083208. Commercially available products include "High Purity Graphite Powder SP-270" and "Artificial Graphite Powder HAG-150" from Nippon Graphite Co., Ltd.

[0182] Carbon black can be produced by pyrolysis or incomplete combustion of hydrocarbons such as oil and natural gas, specifically by methods known as the furnace process, channel process, acetylene process, and pine soot process.

[0183] Activated carbon can be produced by carbonizing and activating wood (e.g., charcoal, sawdust, bark), fruit shells (e.g., coconut shells), grain husks (e.g., rice husks), coal (e.g., peat, tar, coke), petroleum (e.g., tar, pitch), etc. at high temperatures. Commercially available products include "Porous Carbon CNover" from Toyo Tanso Co., Ltd. and "Triporous" from Sony Corporation.

[0184] Alternatively, a nitrogen-doped carbon material can be used as the porous material [S], for example, by the method described in JP 2022-071587 A. The nitrogen-doped carbon material has a nitrogen atom / carbon atom molar ratio of 0.003 to 0.300, preferably 0.004 to 0.200, as measured by X-ray photoelectron spectroscopy (XPS), and satisfies the requirement that the material contains a nitrogen-doped carbon material having a graphene structure into which nitrogen atoms have been substituted or introduced. The nitrogen atom / carbon atom molar ratio is a value obtained by X-ray photoelectron spectroscopy (XPS) measurement, and specifically, it is obtained by calculating the nitrogen atom / carbon atom molar ratio from the peak areas of nitrogen atoms and carbon atoms in the spectrum obtained from the carbon material. A higher nitrogen atom / carbon atom molar ratio is preferable because it promotes coordination with cations generated from the transition metal compound, but if the nitrogen atom / carbon atom molar ratio is too high, the graphene structure in the carbon material tends to decrease. The carbon material is a solid carbon material and is not particularly limited as long as it meets the above requirements, and includes carbon materials that are crystalline, low-crystalline, amorphous, and mixtures thereof. Examples of methods for producing nitrogen-doped carbon materials having a graphene structure in which nitrogen atoms are substituted or introduced include a method of performing plasma treatment on a carbon material in a nitrogen atmosphere, as exemplified in ACS NANO, 2010, 1790, and a method of performing plasma treatment on a cyclic compound containing carbon and nitrogen in its chemical composition and having a ring structure in at least part of its structure, as exemplified in JP-A-2014-100617 and JP-A-2019-189495.

[0185] Examples of organic compounds that can be used include polymers produced mainly from olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; polymers produced mainly from vinylcyclohexane, styrene, and divinylbenzene; and reaction products and modified products thereof.

[0186] Alternatively, for example, a porous coordination polymer can be used as the porous material [S]. The porous coordination polymer is a porous crystalline substance composed of organic ligands and metal ion clusters that occupy the central positions of the structures to which the organic ligands are coordinated, and is also called a metal organic framework (MOF). The porous coordination polymer has a molar ratio of halogen atoms to Group 4 transition metal atoms of the periodic table (halogen atoms / Group 4 transition metal atoms) of 0.20 or more and 1.0 or less, as measured by X-ray photoelectron spectroscopy (XPS), and a specific surface area of ​​500 m2 or less as measured by the BET multipoint method. 2 / g or more 4000m 2 The specific surface area is preferably 1000 m / g or less. 2 / g or more 4000m 2 / g or less. The porous coordination polymer can be produced by any conventionally known production method. Examples of such production methods include a method in which two types of solutions, a solution containing a Group 4 transition metal ion and a solution containing the above-mentioned organic ligand, are gradually diffused and reacted at the liquid-liquid interface; a method in which the above-mentioned organic ligand or a solution thereof is added to a solution containing a Group 4 transition metal ion and reacted with stirring; and a method in which a solution containing a Group 4 transition metal ion and the above-mentioned organic ligand are reacted in a pressure vessel.

[0187] In addition, a solid component obtained by insolubilizing the compound (C) using the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO 2010 / 55652, etc., can also be used as the porous material [S].

[0188] Furthermore, methods described in JP-A-9-12622, WO-01 / 58969, WO-96 / 28480, WO-97 / 19959, JP-A-10-120727, JP-A-10-130316, JP-A-2015-124285, JP-A-2022-69397, and the like have hitherto been known in which a borate compound is immobilized on silica gel by chemically reacting the borate compound with a support such as silica gel in order to provide an olefin polymerization catalyst with the function of a solid catalyst component. By utilizing the hydroxy group of compound (A) of the present invention as a chemical reaction site, compound (A) can be immobilized on a porous material [S] such as the porous oxide, and the olefin polymerization catalyst of the present invention can also be used as a solid catalyst.

[0189] The porous material (S) preferably used in the present invention is The particle size is preferably 1 to 300 μm, more preferably 3 to 100 μm; The specific surface area is preferably 50 to 1300 m 2 / g, more preferably 150 to 1200m 2 / g; The pore volume is preferably 0.3 to 3.0 cm 3 / g, more preferably 0.5 to 2.0 cm 3 / g Such a porous material (S) is dried and / or fired at 100 to 1000°C, preferably 150 to 700°C, as required, before use. The particle shape of the porous material [S] is not particularly limited, but is preferably spherical.

[0190] <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.

[0191] <Instructions and order of addition of each ingredient> During olefin polymerization, the method of use and order of addition of each component can be selected arbitrarily, but the following method is exemplified. Hereinafter, the compound (A) of the present invention, the transition metal complex (B), the compound (C), and the porous material (S) will be referred to as "component (A)," "component (B)," "component (C)," and "component (S)," respectively. (1) A method in which component (A) and component (B) are added to a polymerization reactor in any order. (2) A method of adding component (A), component (B), and component (C) to a polymerization reactor in any order. (3) A method of adding a catalyst component in which component (A) is supported on component (S), and component (B) to a polymerization reactor in any order. (4) A method in which a catalyst component in which component (A) is supported on component (S), component (B), and component (C) are added to a polymerization reactor in any order.

[0192] [Production method of olefin polymer] 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 and compound (C). 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 (4), to polymerize the olefin.

[0193] In 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 solvents 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 solvent may be used alone or in combination of two or more. Alternatively, a so-called bulk polymerization method may be used in which the liquefied olefin to be supplied to the polymerization itself is used as the solvent.

[0194] By using the compound (A) of the present invention, the transition metal complex (B) can be immobilized to the compound (A) or to the porous material (S) via the compound (A) at a higher rate than when a borate compound conventionally used as a co-catalyst in olefin polymerization is used instead of the compound (A). Therefore, in the production of an olefin polymer of the present invention, the method of using the transition metal complex (B) immobilized to the porous material (S) via the compound (A) 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 borate compound was used.

[0195] 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.

[0196] The compound (A) (component (A)) of the present invention 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.

[0197] Component (B) is usually 1 x 10 per liter of reaction volume. -10 ~1×10 -2mol, preferably 1 x 10 -8 ~1×10 -3 It is used in molar amounts.

[0198] Component (C-1) 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. Component (C-2) 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.

[0199] When component (S) is used, it can be used in an amount such that the weight ratio of component (B) to component (S) [(B) / (S)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0200] In the production method 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.

[0201] 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.

[0202] The olefin polymer (e.g., ethylene homopolymer, ethylene / α-olefin copolymer) obtained by the production method 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.

[0203] <Olefin> In one embodiment of the production method of the present invention, the olefin supplied to the polymerization reaction includes ethylene and α-olefins having 3 to 20 carbon atoms.

[0204] 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.

[0205] 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, and more preferably propylene, 1-butene, 1-hexene, and 1-octene. These α-olefins may be used alone or in combination of two or more.

[0206] Furthermore, a non-conjugated polyene may be copolymerized together with ethylene or an α-olefin having 3 to 20 carbon atoms. [Example]

[0207] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples. <Measurement method> [Identification of Group 13 element-containing compound (A)] The structure of the Group 13 element-containing compound (A) is 270 MHz 1 The determination was carried out by measurement using a H-NMR (GSH-270 manufactured by JEOL Ltd.) according to a conventional method.

[0208] [Metal concentration in the supernatant during preparation of solid catalyst component (X)] The metal concentration in the supernatant liquid during the preparation of the solid catalyst component (X) was determined by ICP atomic emission spectrometry (ICP-AES) (ICPS-8100, manufactured by Shimadzu Corporation).

[0209] [Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of olefin polymer] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). They were calculated from the molecular weight distribution curve obtained using a Waters "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph), and the operating conditions were as follows:

[0210] Operating conditions Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, Tosoh Corporation) Mobile phase: o-Dichlorobenzene (ODCB) (Fujifilm Wako Pure Chemical Industries, Ltd., special grade) Detector: differential refractometer (built-in) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume; 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[0211] [1-octene content] The 1-octene content in the ethylene / 1-octene copolymer was measured by FT-IR (FT-IR410 infrared spectrophotometer manufactured by JASCO Corporation).

[0212] Measurement method In FT-IR, the polymers obtained in the examples were heated to 135°C, melt-stretched in a hot press, and then cooled under pressure at room temperature to obtain films, which were used as measurement samples, and the 1-octene content was measured using a calibration curve. The ethylene / 1-octene copolymer samples used for creating the calibration curve were 13 The 1-octene content was determined by C-NMR measurement.

[0213] <Compounds containing Group 13 elements (A)> In the synthesis of the Group 13 element-containing compound (A) described in detail below, hydrogen chloride (approximately 1 mol / L ethyl ether solution) and lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex were purchased from Tokyo Chemical Industry Co., Ltd. and used as they were. Example A1: Synthesis of Group 13 element-containing compound (A-1) 1-Dimethylamino-2-propanol was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0214] A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.30 g of 1-dimethylamino-2-propanol and 15 mL of diethyl ether were added and stirring was initiated. Subsequently, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise while cooling in an ice bath, and the mixture was allowed to return to room temperature and stirred for 2 hours. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 0.41 g of the compound represented by the following formula (A-1'). 1 H NMR (CDCl3) δ1.27(3H), 2.92(6H), 3.11(1H), 4.40(1H), 4.78(1H) ppm

[0215] [ka]

[0216] Next, 0.14 g of the compound represented by the above formula (A-1'), 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 10 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 50 mL reactor and stirred at room temperature for 2 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 hexane and water and then dried under reduced pressure to obtain 0.58 g of a Group 13 element-containing compound represented by the following formula (A-1). 1 H-NMR (CDCl3) δ1.36(3H), 2.19(1H), 2.90-3.10(8H), 4.20(1H) ppm

[0217] [ka]

[0218] [Example A2: Synthesis of Group 13 element-containing compound (A-2)] N,N-Dibenzylethanolamine was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0219] A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.80 g of N,N-dibenzylethanolamine and 10 mL of diethyl ether were added and stirring was initiated. Subsequently, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise while cooling in an ice bath, and the mixture was allowed to return to room temperature and stirred for 2 hours. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 0.78 g of the compound represented by the following formula (A-2'). 1 H-NMR (CDCl3) δ3.10(2H), 3.92(2H), 4.20(2H), 4.41(2H), 7.47(6H), 7.62(4H), 12.07(1H) ppm

[0220] [ka]

[0221] Next, 0.28 g of the compound represented by the above formula (A-2'), 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 15 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 50 mL reactor and stirred at room temperature for 2 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 hexane and water and then dried under reduced pressure to obtain 0.42 g of a Group 13 element-containing compound represented by the following formula (A-2). 1 H-NMR (CDCl3) δ2.25(1H), 3.32(2H), 3.95(2H), 4.26(4H), 6.20(1H), 7.25(4H), 7.55(6H) ppm

[0222] [ka]

[0223] Example A3: Synthesis of Group 13 element-containing compound (A-3) N-lauryldiethanolamine was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0224] In a thoroughly dried, nitrogen-purged 50 mL reactor, 0.50 g of N-lauryldiethanolamine and 15 mL of diethyl ether were added and stirring was initiated. Subsequently, while cooling in an ice bath, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to return to room temperature and stirred for 2 hours. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 0.52 g of the compound represented by the following formula (A-3'). 1H-NMR (CDCl3) δ0.88(3H), 1.10-1.50(18H), 1.85(2H), 3.10-3.50(6H), 4.05(4H), 4.84(2H), 10.38(1H) ppm

[0225] [ka]

[0226] Next, 0.31 g of the compound represented by the above formula (A-3'), 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 50 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 100 mL reactor and stirred at room temperature for 4 hours. Water was added to the resulting suspension, and the organic layer was extracted using a separatory funnel. The solvent was distilled off, and the residue was dried under reduced pressure to obtain 0.70 g of a Group 13 element-containing compound represented by the following formula (A-3). 1 H-NMR (CDCl3) δ0.87(3H), 1.10-1.50(18H), 1.74(2H), 2.33(2H), 3.20(2H), 3.28(4H), 3.97(4H) ppm

[0227] [ka]

[0228] Example A4: Synthesis of Group 13 element-containing compound (A-4) Stearyldiethanolamine was purchased from Tokyo Chemical Industry Co., Ltd. and used as is. A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.80 g of stearyldiethanolamine and 15 mL of diethyl ether were added and stirring was initiated. Subsequently, while cooling in an ice bath, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to return to room temperature and stirred for 2 hours. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 0.75 g of the compound represented by the following formula (A-4'). 1H-NMR (CDCl3) δ0.88(3H), 1.10-1.50(30H), 1.87(2H), 3.10-3.40(6H), 4.06(4H), 4.73(2H), 10.68(1H) ppm

[0229] [ka]

[0230] Next, 0.40 g of the compound represented by the above formula (A-4'), 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 50 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 100 mL reactor and stirred at room temperature for 4 hours. Water was added to the resulting suspension, and the organic layer was extracted using a separatory funnel. The solvent was distilled off, and the residue was dried under reduced pressure to obtain 0.72 g of a Group 13 element-containing compound represented by the following formula (A-4). 1 H-NMR (CDCl3) δ0.87(3H), 1.10-1.50(30H), 1.76(2H), 2.33(2H), 3.10-3.40(6H), 3.98(4H) ppm

[0231] [ka]

[0232] Example A5: Synthesis of Group 13 element-containing compound (A-5) 1-Aminohexane and 1,2-epoxydodecane were purchased from Tokyo Chemical Industry Co., Ltd. and used as they were.

[0233] 2.0 g of 1-aminohexane and 9.5 mL of 1,2-epoxydodecane were added to a thoroughly dried, nitrogen-purged 50 mL reactor, and stirring was continued at 100 °C for 4 days. 1.0 g of the resulting reaction solution was added to a thoroughly dried, nitrogen-purged 50 mL reactor, and 15 mL of diethyl ether was added and stirring was initiated. Subsequently, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise while cooling in an ice bath, and the mixture was returned to room temperature and stirred for 2 hours. After distilling off the solvent, the residue was washed with hexane and dried under reduced pressure to obtain 0.77 g of the compound represented by the following formula (A-5'). 1 H-NMR (CDCl3) δ0.88(9H), 1.00-1.60(42H), 1.82(2H), 2.90-3.40(6H), 4.25(2H), 10.69(1H) ppm

[0234] [ka]

[0235] Next, 0.30 g of the compound represented by the above formula (A-5'), 0.60 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 50 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 100 mL reactor and stirred at room temperature for 4 hours. Water was added to the resulting suspension, and the organic layer was extracted using a separatory funnel. The solvent was distilled off, and the residue was dried under reduced pressure to obtain 0.60 g of a Group 13 element-containing compound represented by the following formula (A-5). 1 H-NMR (CDCl3) δ0.88(9H), 1.10-1.90(44H), 2.15(2H), 2.90-3.30(6H), 3.95(2H) ppm

[0236] [ka]

[0237] [Example A6: Synthesis of Group 13 element-containing compound (A-6)] Triethanolamine hydrochloride was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0238] 0.19 g of triethanolamine hydrochloride, 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 40 mL of water were added to a 100 mL reactor and stirred at room temperature for 1 hour. The insoluble matter in the resulting suspension was collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 0.72 g of the compound represented by the following formula (A-6). 1 H-NMR (CD3OD) δ3.43(6H), 3.89(6H)ppm

[0239] [ka]

[0240] Example A7: Synthesis of Group 13 element-containing compound (A-7) N-butylaniline and 1,2-epoxydodecane were purchased from Tokyo Chemical Industry Co., Ltd. and used as they were.

[0241] 5.0 g of N-butylaniline and 8.1 mL of 1,2-epoxydodecane were added to a thoroughly dried, nitrogen-purged 100 mL reactor, and stirring was continued at 100 °C for 20 days. The resulting reaction solution was then dried. 5.0 g of the resulting residue was transferred to a thoroughly dried, nitrogen-purged 50 mL reactor. 13.5 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was then added dropwise while cooling in an ice bath. The mixture was then returned to room temperature and stirred for 2 hours. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 3.3 g of the compound represented by the following formula (A-7'). 1 H-NMR (CDCl3) δ0.87(6H), 1.24-1.56(22H), 2.03(1H), 3.25-3.78(4H), 5.05(1H), 7.54(3H), 7.78(2H)ppm

[0242] [ka]

[0243] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 2.6 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 20 mL of dichloromethane, and stirring was initiated. Then, 1.0 g of the compound represented by formula (A-7') was added, and stirring was continued overnight at room temperature. 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 a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 2.7 g of a Group 13 element-containing compound represented by formula (A-7) below. 1 H-NMR (CDCl3)δ0.87(6H), 1.24-1.83(22H), 2.22(1H), 3.32-3.55(5H), 7.28(2H), 7.65(3H)ppm

[0244] [ka]

[0245] [Example A8: Synthesis of Group 13 element-containing compound (A-8)] N-Dodecylaniline and 1,2-epoxydodecane were purchased from Tokyo Chemical Industry Co., Ltd., and copper (II) trifluoromethanesulfonate was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as received.

[0246] A 100 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 5.0 g of N-dodecylaniline, 8.1 mL of 1,2-epoxydodecane, and 380 mg of copper(II) trifluoromethanesulfonate and stirred at 80°C for 12 hours. Ethyl ether and water were added to the resulting reaction mixture, and the organic layer was separated using a separatory funnel. The mixture was then dehydrated over magnesium sulfate, filtered, and the filtrate was dried under reduced pressure to remove the solvent. 1.0 g of the resulting residue was added to a 50 mL reactor that had been thoroughly dried and purged with nitrogen. While cooling in an ice bath, 1.8 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise. The mixture was then returned to room temperature and stirred for 1 hour. After removing the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 3.3 g of the compound represented by the following formula (A-8'). 1 H-NMR (CDCl3) δ0.87(6H), 1.20-1.58(38H), 2.01(1H), 3.26-3.75(4H), 5.05(1H), 7.54(3H), 7.75(2H)ppm

[0247] [ka]

[0248] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.6 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 10 mL of dichloromethane, and stirring was initiated. Then, 0.4 g of the compound represented by formula (A-8') was added, and stirring was continued overnight at room temperature. 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 a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.5 g of a Group 13 element-containing compound represented by formula (A-8) below. 1 H-NMR (CDCl3)δ0.88(6H), 1.20-1.55(38H), 2.07(1H), 3.27-4.11(5H), 7.28(2H), 7.65(3H)ppm

[0249] [ka]

[0250] [Example A9: Synthesis of Group 13 element-containing compound (A-9)] N-Dodecylaniline and 1,2-epoxyoctadecane were purchased from Tokyo Chemical Industry Co., Ltd., and copper (II) trifluoromethanesulfonate was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as received.

[0251] A thoroughly dried, nitrogen-purged 100 mL reactor was charged with 1.0 g of N-dodecylaniline, 1.2 g of 1,2-epoxyoctadecane, and 140 mg of copper(II) trifluoromethanesulfonate and stirred at 80°C for 12 hours. Ethyl ether and water were added to the resulting reaction mixture, and the organic layer was separated using a separatory funnel. The mixture was then dehydrated over magnesium sulfate, filtered, and the filtrate was dried under reduced pressure to remove the solvent. The entire residue was added to a thoroughly dried, nitrogen-purged 50 mL reactor. While cooling in an ice bath, 8.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise. The mixture was then returned to room temperature and stirred for 1 hour. After the solvent was removed, the residue was washed with ethyl ether and dried under reduced pressure to obtain 1.2 g of the compound represented by the following formula (A-9'). 1 H-NMR (CDCl3) δ0.87(6H), 1.19-1.59(50H), 2.02(1H), 3.26-3.74(5H), 7.52(3H), 7.75(2H)ppm

[0252] [ka]

[0253] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.6 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 10 mL of dichloromethane, and stirring was initiated. Then, 0.4 g of the compound represented by formula (A-9') was added, and stirring was continued overnight at room temperature. 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 a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.5 g of a Group 13 element-containing compound represented by formula (A-9): 1 H-NMR (CDCl3)δ0.87(6H), 1.19-1.56(50H), 2.17(1H), 3.32-3.71(5H), 7.30(2H), 7.66(3H)ppm

[0254] [ka]

[0255] Comparative Example A10: Synthesis of Group 13 Element-Containing Compound (a-10) Trimethylamine hydrochloride was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as is.

[0256] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.77 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 20 mL of dichloromethane, and stirring was initiated. Then, 0.075 g of trimethylamine hydrochloride was added, and stirring was continued overnight at room temperature. 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 and water and then dried under reduced pressure to obtain 0.40 g of a Group 13 element-containing compound represented by the following formula (a-10). 1 H-NMR(CDCl3) δ1.65(9H,s) ppm

[0257] [ka]

[0258] Comparative Example A11: Synthesis of Group 13 Element-Containing Compound (a-11) 4-Dimethylamino-1-butanol was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0259] A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.30 g of 4-dimethylamino-1-butanol and 15 mL of diethyl ether were added and stirring was initiated. Subsequently, while cooling in an ice bath, 5.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to return to room temperature and stirred for 2 hours. The insoluble matter in the resulting suspension was collected by filtration and dried under reduced pressure to obtain 0.38 g of the compound represented by the following formula (a-11'). 1 H-NMR (CDCl3) δ1.75(2H), 2.00(2H), 2.83(6H), 3.15(2H), 3.74(2H), 11.86(1H) ppm

[0260] [ka]

[0261] 0.078 g of the compound represented by the above formula (a-11'), 0.50 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 30 mL of water were added to a 100 mL reactor and stirred at room temperature for 2 hours. The insoluble matter in the resulting suspension was collected by filtration, washed with hexane, and then dried under reduced pressure to obtain 0.38 g of the compound represented by the following formula (a-11). 1 H-NMR (CD3OD) δ1.61(2H), 1.80(2H), 2.88(6H), 3.13(2H), 3.62(2H) ppm

[0262] [ka]

[0263] Comparative Example A12: Synthesis of Group 13 Element-Containing Compound (a-12) 1-Iodohexane, N-lauryldiethanolamine, and sodium hydride powder (60%, liquid paraffin dispersion) were purchased from Tokyo Chemical Industry Co., Ltd. and used as received.

[0264] A 100 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.68 g of sodium hydride powder and 30 mL of tetrahydrofuran, and stirring was initiated. Subsequently, 2.4 g of N-lauryldiethanolamine was added dropwise while cooling in an ice bath, and the mixture was allowed to return to room temperature and stirred for 2 hours. Subsequently, 5.6 g of 1-iodohexane was added dropwise while cooling again in an ice bath, and the mixture was then heated to 60°C and stirred overnight. The reaction mixture was quenched with 50 mL of water, and the organic layer was separated using a separatory funnel. The solvent was evaporated, and the resulting residue was purified by silica gel column chromatography to yield 1.5 g of the compound represented by the following formula (a-12''). 1 H-NMR (CDCl3) δ0.87 (9H), 1.10-1.70(36H), 2.51(2H), 2.70(4H), 3.41(4H), 3.48(4H) ppm

[0265] [ka]

[0266] Into a thoroughly dried and nitrogen-purged 50 mL reactor, 0.28 g of the compound represented by the above formula (a-12'') and 10 mL of diethyl ether were added, and stirring was initiated. Thereafter, while cooling in an ice bath, 2.0 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was returned to room temperature and stirred for 2 hours. The solvent was distilled off, and the residue was dried under reduced pressure to obtain 0.30 g of the compound represented by the following formula (a-12'). 1 H-NMR (CDCl3) δ0.88 (9H), 1.10-1.90(36H), 3.10-3.40(6H), 3.44(4H), 3.91(4H), 12.29(1H) ppm

[0267] [ka]

[0268] Next, 0.30 g of the compound represented by the above formula (a-12'), 0.63 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex, and 50 mL of dichloromethane were added to a thoroughly dried, nitrogen-purged 100 mL reactor and stirred at room temperature for 4 hours. Water was added to the resulting suspension, and the organic layer was extracted using a separatory funnel. The solvent was distilled off, and the residue was dried under reduced pressure to obtain 0.58 g of a Group 13 element-containing compound represented by the following formula (a-12). 1 H-NMR (CDCl3) δ0.88 (9H), 1.00-1.80(36H), 3.08(2H), 3.23(4H), 3.54(4H), 3.65(4H) ppm

[0269] [ka]

[0270] Comparative Example A13: Synthesis of Group 13 Element-Containing Compound (a-13) N-butylaniline was purchased from Tokyo Chemical Industry Co., Ltd. and used as is. 1-Bromododecane was purchased from Fujifilm Wako Co., Ltd. and used as is. In addition, in Comparative Example A13, Example A14, and Example A15, dimethyl sulfoxide (hereinafter referred to as "DMSO") was purchased from Fujifilm Wako Co., Ltd. and used as is, and potassium hydroxide was purchased from Merck and crushed under anaerobically to form a powder before use.

[0271] A 100 mL reactor was thoroughly dried and purged with nitrogen. 5.0 g of N-butylaniline, 9.6 mL of 1-bromododecane, 3.8 g of potassium hydroxide powder, and 10 mL of DMSO were added and stirred at 90 °C for 7 hours. The resulting reaction mixture was then dried. The reaction mixture was quenched with saturated aqueous ammonium chloride and extracted with two 50 mL portions of dichloromethane. The organic layer was washed twice with 100 mL of water and once with 100 mL of aqueous sodium chloride, then dried over magnesium sulfate powder. The solvent was removed by evaporation under reduced pressure. The reaction mixture was purified by silica gel column chromatography (eluent: hexane / dichloromethane (1:1) mixed solvent). 5.0 g of the mixture was transferred to a 50 mL reactor that was thoroughly dried and purged with nitrogen. While cooling in an ice bath, 23.6 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise. The mixture was then returned to room temperature and stirred for 2 hours. After the solvent was distilled off, the residue was washed with ethyl ether and dried under reduced pressure to obtain 5.5 g of a compound represented by the following formula (a-13'). 1 H-NMR (CDCl3) δ0.86(6H), 1.18-1.23(24H), 3.46-3.52(4H), 7.17(2H), 7.63(3H)ppm

[0272] [ka]

[0273] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 2.6 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 20 mL of dichloromethane, and stirring was initiated. Then, 1.0 g of the compound represented by formula (a-13') was added, and stirring was continued overnight at room temperature. 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 a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 1.5 g of a Group 13 element-containing compound represented by formula (a-13) below. 1H-NMR (CDCl3)δ0.88(6H), 1.18(20H), 1.58(2H), 1.99(2H),3.20-3.50(4H), 7.52(3H), 7.71(2H)ppm

[0274] [ka]

[0275] [Example A14: Synthesis of Group 13 element-containing compound (A-14)] Aniline, 1-bromooctadecane, and copper(II) trifluoromethanesulfonate were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as received. 1,2-epoxyoctadecane was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0276] A 100 mL reactor was thoroughly dried and purged with nitrogen, and 0.9 g of potassium hydroxide powder, 5.4 g of 1-bromooctadecane, and 5 mL of DMSO were added and stirred. A solution of 1.5 g of aniline in 10 mL of DMSO was then added dropwise, and the mixture was stirred overnight at 80 °C. The resulting suspension was quenched with 100 mL of aqueous sodium bicarbonate and extracted twice with 100 mL of diethyl ether. The organic layer was washed twice with 100 mL of water and once with 100 mL of brine. The mixture was then dried over magnesium sulfate, and the solvent was removed by evaporation to obtain the residue. Then, 3.0 g of the residual compound, 3.3 mL of 1,2-epoxyoctadecane, and 310 mg of copper(II) trifluoromethanesulfonate were added to a 100 mL reactor that had been thoroughly dried and purged with nitrogen, and stirring was continued at 80°C for 12 hours. Ethyl ether and water were added to the resulting reaction solution, and the organic layer was extracted using a separatory funnel. The solution was then dehydrated over magnesium sulfate, filtered, and the filtrate was dried under reduced pressure to distill off the solvent, yielding 4.7 g of the residual compound. The residual compound was separated by column chromatography into a compound represented by the following formula (A-14″) and a by-product represented by the following formula (a-19″). 1H-NMR ((A-14''),CDCl3)δ0.88(6H,t), 1.26-1.57(62H,m), 2.15(1H,brs), 3.24(2H,t), 3.32-3.34(2H,d), 3.88(1H,m), 6.62-6.64(1H,m), 6.76(2H,d), 7.20(3H,t)ppm 1 H-NMR ((a-19''),CDCl3)δ0.88(6H,t), 1.21-1.35(30H,m), 1.55(4H,m), 3.22(4H,t), 6.62-6.64(2H,d), 7.19(3H,t)ppm

[0277] [ka]

[0278] [ka]

[0279] In a thoroughly dried, nitrogen-purged 50 mL reactor, 0.3 g of the compound represented by the above formula (A-14") and 10 mL of diethyl ether were added and stirred, and while cooling in an ice bath, 0.7 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was returned to room temperature and continued stirring for 1 hour. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 0.3 g of the compound represented by the following formula (A-14'). 1 H-NMR (CDCl3)δ0.88(6H,t),1.25-1.57(62H,m),2.02(1H,br s),3.17-3.76(5H, m),7.52-7.75(5H,m)ppm

[0280] [ka]

[0281] A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.3 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 5 mL of dichloromethane were added and stirring was initiated. A solution of 0.3 g of the compound represented by formula (A-14') above dissolved in 10 mL of dichloromethane was then added dropwise, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.4 g of a Group 13 element-containing compound represented by formula (A-14) below. 1 H-NMR (CDCl3)δ0.88(6H,t), 1.25-1.61(62H,m), 2.27(1H,brs), 3.21-3.53(5H,m), 7.30-7.62(5H,m)ppm

[0282] [ka]

[0283] [Example A15: Synthesis of Group 13 element-containing compound (A-15)] 1-Bromooctadecane and copper(II) trifluoromethanesulfonate were purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as received. 4-Octylaniline and 1,2-epoxyoctadodecane were purchased from Tokyo Chemical Industry Co., Ltd. and used as they were.

[0284] A 100 mL reactor was thoroughly dried and purged with nitrogen, and 1.1 g of potassium hydroxide powder, 3.3 g of 1-bromooctadecane, and 5 mL of DMSO were added and stirred. A solution of 2.0 mL of 4-octylaniline in 10 mL of DMSO was then added dropwise, and the mixture was stirred overnight at 90°C. The resulting suspension was quenched with 100 mL of aqueous sodium bicarbonate and extracted twice with 100 mL of diethyl ether. The organic layer was washed twice with 100 mL of water and once with 100 mL of brine, then dried over magnesium sulfate. The solvent was then removed by evaporation to obtain the residue. Then, 1.3 g of the residual compound, 1.1 mL of 1,2-epoxyoctadodecane, and 100 mg of copper (II) trifluoromethanesulfonate were added to a 100 mL reactor that had been thoroughly dried and purged with nitrogen, and the mixture was stirred at 80°C for 8 hours. Ethyl ether and water were added to the resulting reaction solution, and the organic layer was extracted using a separatory funnel. The solution was then dehydrated over magnesium sulfate and filtered, and the filtrate was dried under reduced pressure to distill off the solvent, yielding 1.5 g of a compound represented by the following formula (A-15″). 1 H-NMR (CDCl3)δ0.88(9H,t), 1.26-1.56(74H,m), 2.31(1H,brs), 2.50(2H,t), 3.02-3.84(5H,m), 6.71-6.72(2H,d), 7.02-7.05(2H,d)ppm

[0285] [ka]

[0286] Into a thoroughly dried, nitrogen-purged 50 mL reactor, 1.5 g of the compound represented by the above formula (A-15") and 10 mL of diethyl ether were added and stirred, and while cooling in an ice bath, 3.1 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was returned to room temperature and continued stirring for 1 hour. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 0.9 g of the compound represented by the following formula (A-15'). 1 H-NMR (CDCl3)δ0.88(9H,t), 1.19-1.62(74H,m), 2.00(1H,brs), 2.64(2H,t), 3.22-3.75(5H,m), 7.30-7.33(2H,d), 7.62-7.64(2H,d)ppm

[0287] [ka]

[0288] A 50 mL reactor was thoroughly dried and purged with nitrogen, and 0.7 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 5 mL of dichloromethane were added and stirring was initiated. A solution of 0.6 g of the compound represented by formula (A-15') above dissolved in 10 mL of dichloromethane was then added dropwise, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.4 g of a Group 13 element-containing compound represented by formula (A-15) below. 1 H-NMR (CDCl3)δ0.88(9H,t), 1.25-1.63(74H,m), 2.13(1H,brs), 2.69(2H,t), 3.25-3.52(5H, m), 7.14-7.16(2H,d), 7.38-7.40(2H,d)ppm

[0289] [ka]

[0290] [Example A16: Synthesis of Group 13 element-containing compound (A-16)] (N-methylanilino)ethanol was purchased from Tokyo Chemical Industry Co., Ltd. and used as received.

[0291] In a thoroughly dried and nitrogen-purged 50 mL reactor, 2.0 g of (N-methylanilino)ethanol and 5 mL of diethyl ether were added, followed by stirring. While cooling in an ice bath, 19.8 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 1 hour. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 1.7 g of the compound represented by the following formula (A-16'). 1 H-NMR (CDCl3)δ3.30(3H,s), 3.69-3.88(4H,m), 1.00(1H,brs), 7.52(3H,t), 7.79-7.81(2H,d)ppm

[0292] [ka]

[0293] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 1.0 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 10 mL of dichloromethane, and stirring was initiated. A solution of 0.3 g of the compound represented by formula (A-16') above dissolved in 15 mL of dichloromethane was then added dropwise, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.8 g of a Group 13 element-containing compound represented by formula (A-16) below. 1 H-NMR (CDCl3)δ3.31(3H,s), 3.64-3.77(4H,m), 7.51-7.60(5H,m)ppm

[0294] [ka]

[0295] [Example A17: Synthesis of aluminum-containing compound (A-17)] 1-Bromopentafluorobenzene and aluminum trichloride were purchased from Fujifilm Wako Pure Chemical Industries, Ltd., and 1.6 M n-butyllithium / hexane solution was purchased from Kanto Chemical Co., Ltd. and used as is.

[0296] A 100 mL reactor was thoroughly dried and purged with nitrogen, and 3.0 g of 1-bromopentafluorobenzene and 30 mL of diethyl ether were added and stirred. The mixture was then cooled to -78°C, and 7.7 mL (1.0 equivalent) of a 1.6 M n-butyllithium / hexane solution was slowly added dropwise, followed by stirring for 3 hours. 0.4 g (0.25 equivalent) of aluminum trichloride was dissolved in 3.0 mL of diethyl ether and slowly added dropwise. 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 a glass filter, and the solvent was distilled off. The residue was washed with hexane, filtered, and dried under reduced pressure to obtain 2.0 g of the compound represented by the following formula (A-17'). MS(ESI,m / z)[M]694.9(found),694.9(calcd)

[0297] [ka]

[0298] Into a thoroughly dried, nitrogen-purged 50 mL reactor, 0.6 g of the compound represented by the above formula (A-17') and 10 mL of dichloromethane were added and stirring was initiated. Then, 0.5 g of the compound represented by (A-7') from Example A7 was added, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.7 g of a Group 13 element-containing compound represented by the following formula (A-17). 1 H-NMR (CDCl3)δ0.86(6H,t), 1.19-1.71(22H,m), 3.22-3.48(5H,m), 7.44(2H,m), 7.58(3H,m)ppm

[0299] [ka]

[0300] [Example A18: Synthesis of Group 13 element-containing compound (A-18)] Bis(4-(2,4,4-trimethylpentan-2-yl)phenyl)amine was purchased from Combi-blocks and used as is. 1,2-epoxyoctadecane was purchased from Tokyo Chemical Industry Co., Ltd. and used as is. Copper(II) trifluoromethanesulfonate was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. and used as is.

[0301] 3.0 g of bis(4-(2,4,4-trimethylpentan-2-yl)phenyl)amine, 2.9 mL of 1,2-epoxyoctadecane, and 280 mg of copper(II) trifluoromethanesulfonate were added to a 100 mL reactor that had been thoroughly dried and purged with nitrogen, and the mixture was stirred at 90°C for 8 hours. Ethyl ether and water were added to the resulting reaction solution, and the organic layer was extracted using a separatory funnel. The solution was then dehydrated over magnesium sulfate and filtered. The filtrate was dried under reduced pressure to remove the solvent, yielding 4.7 g of the compound represented by the following formula (A-18″). 1 H-NMR (CDCl3)δ0.74(18H,s), 0.88(3H,t),1.26(30H,m), 1.35(12H,s), 1.70(4H,s), 2.17(1H,brs), 3.53-3.86(3H,m), 6.92-6.94(2H,d), 7.23-7.25(2H,d)ppm

[0302] [ka]

[0303] 0.3 g of the compound represented by the above formula (A-18") and 10 mL of diethyl ether were added to a 50 mL reactor that had been thoroughly dried and purged with nitrogen, and the mixture was stirred. While cooling in an ice bath, 0.7 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to return to room temperature and continued stirring for 1 hour. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 0.3 g of the compound represented by the following formula (A-18'). 1 H-NMR (CDCl3)δ0.74(18H,s), 0.88(3H,t), 1.26(26H,m), 1.48(12H,s), 1.69(4H,s), 3.44-4.01(7H,m), 7.44-7.47(4H,d), 7.67-7.69(4H,d)ppm

[0304] [ka]

[0305] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.3 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 5 mL of dichloromethane, and stirring was initiated. A solution of 0.3 g of the compound represented by formula (A-18') above dissolved in 5 mL of dichloromethane was then added dropwise, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.4 g of a Group 13 element-containing compound represented by formula (A-18) below. 1 H-NMR (CDCl3)δ0.70(18H,s), 0.88(3H,t), 1.27(26H,m), 1.36(12H,s), 1.72(4H,s), 2.10(1H,brs), 3.46-4.03(7H,m), 7.23(4H,m), 7.42(4H,m)ppm

[0306] [ka]

[0307] Comparative Example A19: Synthesis of Group 13 Element-Containing Compound (a-19) A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.3 g of the compound (a-19") obtained in Example A14 and 5 mL of diethyl ether, and the mixture was stirred. While cooling in an ice bath, 0.8 mL of hydrogen chloride (approximately 1 mol / L ethyl ether solution) was added dropwise, and the mixture was allowed to return to room temperature and continued stirring for 1 hour. After distilling off the solvent, the residue was washed with ethyl ether and dried under reduced pressure to obtain 0.3 g of the compound represented by the following formula (a-19'). 1 H-NMR (CDCl3)δ0.88(6H,t), 1.18-1.25(30H,m), 2.01(4H,m), 3.45(4H, m), 7.51(3H,m), 7.72(2H,m)ppm

[0308] [ka]

[0309] A 50 mL reactor that had been thoroughly dried and purged with nitrogen was charged with 0.3 g of lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex and 5 mL of dichloromethane, and stirring was initiated. A solution of 0.3 g of the compound represented by formula (a-19') above dissolved in 10 mL of dichloromethane was then added dropwise, and stirring was continued overnight at room temperature. The insoluble matter in the resulting suspension was removed by passing it through a glass filter, and the solvent was distilled off. The residue was washed with a mixed solvent of hexane and dichloromethane and then dried under reduced pressure to obtain 0.4 g of a Group 13 element-containing compound represented by formula (a-19) below. 1 H-NMR (CDCl3)δ0.88(6H,t), 1.16-1.63(34H,m), 3.38-3.48(4H,m), 7.37-7.39(2H,m), 7.59-7.60(3H,m)ppm

[0310] [ka]

[0311] [Group 13 element-containing compound (a-20)] N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate represented by the following formula (a-20) was purchased from Tokyo Chemical Industry Co., Ltd. and used as is.

[0312] [ka]

[0313] <Transition metal compound (B)> As the transition metal compound (B), a transition metal compound (B-1) represented by the following formula (B-1), a transition metal compound (B-2) represented by the following formula (B-2), and a transition metal compound (B-3) represented by the following formula (B-3), which were produced by conventionally known methods, were used.

[0314] [ka]

[0315] <Porous material (S)> As the porous material (S), the following porous material (S-1) was used. Porous material (S-1): Silica gel (Fuji Silysia Chemical, average particle size: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3cm 3 / g)

[0316] <Ethylene polymerization using Group 13 element-containing compound (A)> [Example P1] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and ethylene was then supplied at 100 L / hr to saturate the reactor with ethylene. Polymerization was then initiated by adding 0.20 mmol of organometallic compound (C-1) (triisobutylaluminum), 0.015 μmol of the transition metal compound (B-1), and 0.060 μmol of the Group 13 element-containing compound (A-1) obtained in Example A1. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out at 50°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by adding 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 0.88 g of olefin polymer. The Mw of the resulting olefin polymer was 7,110,000.

[0317] [Examples P2 to P9] Polymerization was carried out in the same manner as in Example P1, except that the Group 13 element-containing compounds (A-2) to (A-9) obtained in Examples A2 to A9 were used instead of the Group 13 element-containing compound (A-1), to obtain olefin polymers. The weights of the obtained olefin polymers are shown in Tables 1-1 and 1-2.

[0318] [Comparative Examples P10 to P13] Polymerization was carried out in the same manner as in Example P1, except that the Group 13 element-containing compounds (a-10) to (a-13) obtained in Comparative Examples A10 to A13 were used instead of the Group 13 element-containing compound (A-1), to obtain an olefin polymer. The weights of the obtained olefin polymers are shown in Table 1-2.

[0319] [Examples P19 to P22 and Comparative Example P24] Polymerization was carried out in the same manner as in Example P1, except that the Group 13 element-containing compounds (A-14) to (A-17) obtained in Examples A14 to A17 or (a-19) obtained in Comparative Example a19 were used instead of the Group 13 element-containing compound (A-1), to obtain an olefin polymer. The weight of the obtained olefin polymer is shown in Table 1-3.

[0320] [Example P23 and Comparative Examples P25 to P26] Polymerization was carried out in the same manner as in Example P1, except that 0.150 μmol of the Group 13 element-containing compound (A-18) obtained in Example A18 and the Group 13 element-containing compounds (a-13) and (a-19) obtained in Comparative Examples a13 and a19 were used instead of 0.060 μmol of the Group 13 element-containing compound (A-1), to obtain an olefin polymer. The weight of the obtained olefin polymer is shown in Table 1-4.

[0321] The evaluation results of Examples P1 to P9 and Comparative Examples P10 to P13, and Examples P19 to P23 and Comparative Examples P24 to P26 are shown in Tables 1-1 to 1-4. Note that "polymerization activity" in Tables 1-1 to 1-4 indicates the yield (kg) of olefin polymer per 1 mmol of total transition metal atoms (M=Zr) in the transition metal complex (B) per unit time (hr).

[0322] [Table 1-1]

[0323] [Table 1-2]

[0324] [Table 1-3]

[0325] [Table 1-4]

[0326] <Ethylene / 1-octene copolymerization using Group 13 element-containing compound (A)> [Example P14] A 1 L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 470 mL of heptane, 30 mL of 1-octene, and 0.30 mmol of organometallic compound (C-1) (triisobutylaluminum) under a nitrogen atmosphere. Ethylene was then added to saturate the reactor. Next, the temperature and pressure were raised to 80°C and 0.8 MPaG with ethylene while stirring. Then, 0.050 μmol of the transition metal compound (B-2) and 0.50 μmol of the Group 13 element-containing compound (A-3) obtained in Example A3 were added to initiate polymerization. Polymerization was carried out for 10 minutes at 80°C and 0.8 MPaG, followed by the addition of a small amount of methanol to terminate the polymerization. After polymerization, the reaction mixture was added to 1 L of a 1 / 3 methanol / acetone mixed solvent containing a small amount of hydrochloric acid to precipitate an olefin polymer. The resulting precipitate was filtered and dried under reduced pressure at 80°C for 10 hours, yielding 4.97 g of olefin polymer. The resulting olefin polymer had a Mw of 6,860,000 and a 1-octene content of 19.2 mol %.

[0327] [Comparative Example P15] Polymerization was carried out in the same manner as in Example P14, except that the Group 13 element-containing compound (a-10) obtained in Comparative Example A10 was used instead of the Group 13 element-containing compound (A-3), to obtain an olefin polymer. The weight of the obtained olefin polymer is shown in Table 2.

[0328] The evaluation results of Example P14 and Comparative Example P15 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).

[0329] [Table 2]

[0330] The results in Tables 1-1 to 1-4 and Table 2 show that when the Group 13 element-containing compounds (A-1) to (A-9) and (A-14) to (A-18) of the present invention were used, more olefin polymers were obtained than in the comparative examples using the Group 13 element-containing compounds (a-10) to (a-13) and (a-19) that do not have a hydroxy group at the position shown in general formula (I).

[0331] <Preparation of solid catalyst component (X) containing group 13 element-containing compound (A) and transition metal compound (B) and olefin polymerization using solid catalyst component (X)> [Example P16] A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of porous material (S-1) and 20 mL of toluene. Stirring was initiated using a rotor. 0.40 mL of a toluene solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) was added to the suspension. Stirring was continued at room temperature for 60 minutes, after which the stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with toluene. Next, a toluene solution of 0.020 mmol of the Group 13 element-containing compound (A-1) obtained in Example A1 was added, and stirring was continued at room temperature for 60 minutes, after which the stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with heptane. 5.0 mL of a heptane solution of transition metal compound (B-3) (1.0 mmol / L in terms of titanium atoms) was added to the suspension, and the suspension was stirred at room temperature for 30 minutes, resulting in a suspension with a solids concentration of porous material (S-1) of 10 g / L. After stopping the stirring and allowing the solids in the suspension to settle, a portion of the supernatant liquid containing no solids was collected and analyzed. The Ti concentration was found to be below the detection limit (<0.021 μmol / mL). The supernatant liquid was then decanted and heptane was added repeatedly to prepare a suspension of the solid catalyst component (X-1) with a solid concentration of 10 g / L of the porous material (S-1). A 1-liter stainless steel autoclave was thoroughly purged with nitrogen and, under a nitrogen atmosphere, 500 mL of heptane was added. Ethylene was then passed through to saturate the reactor. Next, 0.38 mmol of organometallic compound (C-1) (triisobutylaluminum) and 4.0 mL of the solid catalyst component (X-1) suspension were added with stirring. The temperature and pressure were raised to 80°C and 0.8 MPaG, and the polymerization reaction was carried out with ethylene for 90 minutes. After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours, yielding 17.2 g of olefin polymer powder. The resulting polymer had an Mw of 2,510,000 and an Mw / Mn ratio of 4.5.

[0332] [Example P17] A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of porous material (S-1) and 20 mL of toluene. Stirring was initiated using a rotor. 0.40 mL of a toluene solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) was added to the suspension. Stirring was continued at room temperature for 60 minutes, after which the stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with toluene. Next, a toluene solution of 0.020 mmol of the Group 13 element-containing compound (A-3) obtained in Example A3 was added, and stirring was continued at room temperature for 60 minutes. The stirring was then stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with heptane. 5.0 mL of a heptane solution of transition metal compound (B-3) (1.0 mmol / L in terms of titanium atoms) was added to the suspension, and the suspension was stirred at room temperature for 30 minutes, resulting in a suspension with a solids concentration of 10 g / L of porous material (S-1). After stopping the stirring and allowing the solids in the suspension to settle, a portion of the supernatant liquid containing no solids was collected and analyzed. The Ti concentration was found to be below the detection limit (<0.021 μmol / mL). The supernatant liquid was then decanted and heptane was added repeatedly to prepare a suspension of the solid catalyst component (X-2) with a solid concentration of 10 g / L of the porous material (S-1). A polymerization reaction was carried out in the same manner as in Example P16, except that solid catalyst component (X-2) was used instead of solid catalyst component (X-1). After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain 30.8 g of an olefin polymer powder. The weight of the obtained olefin polymer is shown in Table 3-1.

[0333] [Comparative example P18] A 30 mL Schlenk flask was thoroughly purged with nitrogen and charged with 200 mg of porous material (S-1) and 20 mL of toluene. Stirring was initiated using a rotor. 0.40 mL of a toluene solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) was added to this suspension. Stirring was continued at room temperature for 60 minutes, after which the stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with toluene. Next, a toluene solution of 0.020 mmol of the Group 13 element-containing compound (a-10) obtained in Comparative Example A10 was added, and stirring was continued at room temperature for 60 minutes, after which the stirring was stopped and the suspension was allowed to stand. The supernatant was removed by decantation, and the suspension was washed twice with heptane. 5.0 mL of a heptane solution of transition metal compound (B-3) (1.0 mmol / L in terms of titanium atoms) was added to this suspension, and the suspension was stirred at room temperature for 30 minutes to prepare a suspension with a solid concentration of porous material (S-1) of 10 g / L. After stopping the stirring and allowing the solids in the suspension to settle, a portion of the solid-free supernatant was collected and analyzed, revealing a Ti concentration of 0.22 μmol / mL. The supernatant was then decanted and heptane was added repeatedly to prepare a suspension of the solid catalyst component (X-3) with a solid concentration of 10 g / L of the porous material (S-1). A polymerization reaction was carried out in the same manner as in Example P16, except that solid catalyst component (X-3) was used instead of solid catalyst component (X-1). After the reaction was completed, the contents of the reactor were filtered and dried under reduced pressure at 80°C for 10 hours to obtain 0.80 g of an olefin polymer powder. The weight of the obtained olefin polymer is shown in Table 3-1.

[0334] The evaluation results of Examples P16 and P17 and Comparative Example P18 are shown in Table 3-1. In Table 3-1, "polymerization activity" indicates the yield (g) of olefin polymer per 1 g of the solid catalyst component (X) prepared and used in Examples P16 to P18.

[0335] [Table 3-1]

[0336] [Examples P27 to P29 and Comparative Examples P30 to P31] Solid catalyst component suspensions (X-4) to (X-8) were prepared and polymerization reactions were carried out in the same manner as in Examples P16 to P18, except that Group 13 element-containing compounds (A-1), (A-3), (A-7), (a-10), and (a-20) were used, and a heptane solution (1.0 mmol / L in terms of zirconium atoms) premixed with transition metal compound (B-1) and organometallic compound (C-1) (triisobutylaluminum) 0.15 mmol was used instead of transition metal compound (B-3). The Zr concentration of the solid-free supernatant and the weight of the resulting polymer powder are shown in Table 3-2. The "polymerization activity" in Table 3-2 indicates the yield (g) of olefin polymer per gram of solid catalyst component (X) added during the polymerization reaction.

[0337] [Table 3-2]

[0338] The results in Tables 3-1 and 3-2 show that when the Group 13 element-containing compound of the present invention was used, a larger amount of the transition metal compound (B) could be immobilized on the solid catalyst component (X) and a larger amount of olefin polymer was obtained, compared to the comparative examples in which the Group 13 element-containing compounds (a-10) and (a-20) not having a hydroxy group at the position shown in general formula (I) were used.

Claims

1. A compound (A) containing a Group 13 element represented by the following general formula (A): [R １ R ２ R ３ NH] ＋ [MQ ４ ] － …(A) (In general formula (A), R １ , R ２ and R ３ are each independently a hydrocarbon group having 1 to 30 carbon atoms or a substituent represented by the following general formula (I): R １ , R ２ and R ３ At least one of the groups is a substituent represented by the following general formula (I). M is an atom of a Group 13 element. Each of the four Qs is independently an aryl group having 6 to 20 carbon atoms and represented by the following general formula (Q1): 【Chemical 1】 (In the above general formula (I), * represents a bond to a nitrogen atom. Multiple R's ａ are each independently a hydrocarbon group having from 1 to 30 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a sulfanyl group, or a heteroatom-containing hydrocarbon group, The heteroatom-containing hydrocarbon group is a dimethylamino group, a diethylamino group, a pyrrolyl group, a pyridyl group, an indolyl group, an indolinyl group, a carbazolyl group, a benzimidazolyl group, or a benzoxazolyl group. 【Chemistry 2】 (In general formula (Q1), * represents a bond to an atom of a Group 13 element. The plurality of R's each independently represent a substituent (rq1) selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, and a halogen-containing hydrocarbon group, or a hydrogen atom, and the halogen-containing hydrocarbon group is a trifluoromethyl group, a pentafluoroethyl group, or a pentafluorophenyl group. At least one of the R adjacent to * is the substituent (rq1). When a plurality of the substituents (rq1) are present, the plurality of substituents (rq1) may be the same as or different from one another. The plurality of substituents (rq1) may be bonded to one another to form an aromatic ring which may have a substituent, or may not be bonded to one another.

2. The Group 13 element-containing compound (A) according to claim 1 , wherein in the general formula (A), M is a boron atom.

3. A catalyst for olefin polymerization comprising the Group 13 element-containing compound (A) according to claim 1, a transition metal complex (B), and at least one compound (C) selected from the group consisting of organometallic compounds (C-1) and organoaluminum oxy compounds (C-2).

4. The olefin polymerization catalyst according to claim 3, further comprising a porous material (S).

5. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 3 or 4.

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