Novel borate compound

Abstract

The purpose of the present invention is to provide a borate compound which is useful as a co-catalyst that is used for polymerization of olefins or dienes. The present invention relates to: a borate compound which is represented by formula (1) (wherein the symbols are as defined in the description); and use of the borate compound as a co-catalyst for polymerization of olefins or dienes.

Description

Technical Field

[0001] The present invention relates to borate compounds useful as cocatalysts for the polymerization of olefins and dienes, and methods for producing them.

Background Art

[0002] Conventionally, many reports have been made on the use of non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for the polymerization of olefins and dienes. As cocatalysts used to stabilize the cationic active species of these metal complex catalysts, aluminoxanes (MAO) such as alkylaluminum and methylaluminoxane, Bronsted acid salts such as ammonium borate, and Lewis acid salts such as triphenylcarbenium borate have been used (Non-Patent Document 1).

[0003] In the catalytic activation reaction by the Bronsted acid salt, the leaving group on the metal complex catalyst is protonated, detached from the metal complex catalyst, and a cationic active species of the metal complex catalyst is generated. Thereby, a non-coordinating anion derived from the Bronsted acid salt stabilizes the active species. As the Bronsted base constituting the Bronsted acid salt, various borate compounds such as tetrakis(pentafluorophenyl)borate, which is a non-coordinating anion, have been reported (Non-Patent Document 1). As the Bronsted acid, Bronsted acids containing nitrogen, phosphorus, oxygen, and / or sulfur are known (Patent Document 1).

[0004] As the Bronsted acid salt, Bronsted acid salts containing nitrogen (ammonium borate) such as dimethylanilinium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, and methylpyrrolidinium tetrakis(pentafluorophenyl)borate are known (Patent Document 2). In the catalytic activation reaction using these ammonium borates, an amine compound is generated by losing a proton at the protonation stage. Such an amine compound may interact with the cationic active species of the metal complex catalyst, and in that case, there is concern that it may have an adverse effect on the polymerization reaction.

[0005] In addition, as the solvent used in the polymerization, a nonpolar hydrocarbon solvent is used. In particular, from the viewpoints of odor and toxicity, there is a growing trend to switch to aliphatic hydrocarbon solvents such as n-hexane rather than aromatic hydrocarbon solvents such as toluene.

[0006] However, ordinary tetrakis(pentafluorophenyl)borate compounds are known to be poorly soluble in aromatic hydrocarbon solvents such as toluene, or even if dissolved, the borate compound separates into a liquid-liquid two-phase of a concentrated phase in which the borate compound is dissolved and a dilute phase in which it is not dissolved (Patent Document 3).

[0007] In addition, since tetrakis(pentafluorophenyl)borate compounds are poorly soluble in aliphatic hydrocarbon solvents such as n-hexane and n-heptane, compounds soluble in aliphatic hydrocarbon solvents have been desired and proposed (Patent Document 4). Di(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate and bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate described in Patent Document 4 are useful as compounds soluble in hydrocarbon solvents.

[0008] However, when using bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borate or bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate described in Patent Document 4, there is a concern that the trialkylamine generated after the catalyst activation reaction may be a catalyst poison for the polymerization reaction of olefins and dienes because the trialkylamine has nucleophilicity.

Prior Art Documents

Non-Patent Documents

[0009]

Non-Patent Document 1

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0011] In view of these prior arts, the present invention provides a borate compound that is soluble in a hydrocarbon solvent and useful as a cocatalyst for the polymerization reaction of olefins and dienes, and an industrial production method thereof.

Means for Solving the Problems

[0012] As a result of intensive studies, the present inventors have found that the following formula (1):

[0013]

Chemical Formula

[0014] [wherein, R 1 , R 2 , R 3 and R 4 each independently represents a C 1-4 aryl group substituted with one or more fluorine atoms or fluorinated C 6-14 alkyl groups, [A + -H] represents a cation in which the ring nitrogen atom of a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound having 25 or more carbon atoms and substituted with two or more identical or different C 1-30 alkyl groups or C 1-30 alkoxy groups is protonated.] The compound represented by the following formula (hereinafter also referred to as "the compound of the present invention") does not generate a compound that poisons the catalyst for the polymerization reaction of olefins and dienes, and has been found to be useful as a cocatalyst for the polymerization reaction of olefins and dienes for the first time, leading to the completion of the present invention.

[0015] That is, the present invention is as follows. [1] The following formula (1):

[0016] [Chemical formula]

[0017] [wherein, R 1 , R 2 , R 3 and R 4 each independently represents a C 1-4 aryl group substituted with one or more fluorine atoms or fluorinated C 6-14 alkyl groups, [A + -H] represents a cation in which the ring nitrogen atom of a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound having 25 or more carbon atoms and substituted with two or more identical or different C 1-30 alkyl groups or C 1-30 alkoxy groups is protonated.] The compound represented by the formula. [2] R1 , R 2 , R 3 and R 4 and R are each independently one or more phenyl groups, 1-naphthyl groups, 2-naphthyl groups, 2-biphenylyl groups, 3-biphenylyl groups, 4-biphenylyl groups, 1-anthryl groups, 2-anthryl groups, 9-anthryl groups, 9-phenanthryl groups or 3-phenanthryl groups, each substituted with a fluorine atom or a trifluoromethyl group, the compound according to [1] above. [3]R 1 , R 2 , R 3 and R 4 and R are all pentafluorophenyl groups, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) groups, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl groups or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl groups, the compound according to [1] above. [4]A is a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound having 25 or more carbon atoms in total, substituted with two identical or different C 9-30 alkyl groups or C 9-30 alkoxy groups, the compound according to any one of [1] to [3] above. [5]The 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound is pyridine or imidazole, the compound according to [4] above. [6]A cocatalyst for the polymerization of at least one monomer selected from the group consisting of olefins and dienes, comprising the compound according to any one of [1] to [5] above. [7]A method for producing a polymer, comprising polymerizing at least one monomer selected from the group consisting of olefins and dienes using the compound according to any one of [1] to [5] above as a cocatalyst. [Advantages of the Invention]

[0018] According to the present invention, the borate compound which is soluble in a hydrocarbon solvent and useful as a cocatalyst for the polymerization reaction of olefins and dienes can be provided. [Embodiments for Carrying Out the Invention]

[0019] The definitions of the terms and symbols used in this specification are described below.

[0020] In this specification, the "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0021] In this specification, the "alkyl (group)" means a linear or branched alkyl group having 1 or more carbon atoms.

[0022] In this specification, "C 1-30 alkyl (group)" means a linear or branched alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, etc.

[0023] In this specification, "C 9-30 alkyl (group)" means a linear or branched alkyl group having 9 to 30 carbon atoms, for example, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, etc.

[0024] In this specification, "C 1-6"Alkyl (group)" means a linear or branched alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. Among them, C 1-4 alkyl group is preferred.

[0025] In this specification, "halo C 1-6 alkyl (group)" means a group in which one or more hydrogen atoms in the above-mentioned "C 1-6 alkyl" group are substituted with halogen. Specifically, for example, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc. Among them, "halo C 1-4 alkyl" is preferred.

[0026] In this specification, "fluoro C 1-6 alkyl (group)" means a group in which the halogen atom in the above-mentioned "halo C 1-6 alkyl" group is a fluorine atom. Specifically, for example, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc. Among them, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, etc. of "fluoro C1-4 "Alkyl (group)" is preferred, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl or pentafluoroethyl is more preferred, and trifluoromethyl is particularly preferred.

[0027] In this specification, "cycloalkyl (group)" means a cyclic alkyl group, and particularly when there is no limitation on the carbon number range, preferably C 3-8 It is a cycloalkyl group.

[0028] In this specification, "C 3-8 cycloalkyl (group)" means a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Among them, C 3-6 cycloalkyl group is preferred.

[0029] In this specification, "alkoxy (group)" means a group in which a linear or branched alkyl group is bonded to an oxygen atom.

[0030] In this specification, "C 1-30 alkoxy (group)" means a linear or branched alkoxy group having 1 to 30 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, triacontyloxy and the like.

[0031] In this specification, "C9-30 "Alkoxy (group)" means a linear or branched alkoxy group having 9 to 30 carbon atoms, and examples thereof include nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, nonadecyloxy, eicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, triacontyloxy and the like.

[0032] In this specification, "C" 1-6 "Alkoxy (group)" means a linear or branched alkoxy group having 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like. Among them, a C 1-4 alkoxy group is preferred.

[0033] In this specification, "halo C" 1-6 "Alkoxy (group)" means a group in which one or more hydrogen atoms in the above-mentioned "C" 1-6 alkoxy group are substituted with halogen atoms. Specifically, for example, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, 5,5,5-trifluoropentyloxy, 6,6,6-trifluorohexyloxy and the like can be mentioned. Among them, "halo C" 1-4 alkoxy is preferred.

[0034] In this specification, "fluoro C" 1-6 "Alkoxy (group)" means the above-mentioned "halo C" 1-6It means a group in which the halogen atom in the "alkoxy" group is a fluorine atom. Specifically, for example, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, 5,5,5-trifluoropentyloxy, 6,6,6-trifluorohexyloxy, etc. may be mentioned. Among them, "fluoro C 1-4 alkoxy (group)" is preferred, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy or pentafluoroethoxy is more preferred, and trifluoromethoxy is particularly preferred.

[0035] In the present specification, the "aryl (group)" means a monocyclic or polycyclic (condensed) hydrocarbon group showing aromaticity. Specifically, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl, 9-phenanthryl, etc. C 6-14 aryl groups may be mentioned. Among them, phenyl, 1-naphthyl or 2-naphthyl is preferred.

[0036] In the present specification, the "5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound" means a 5- or 6-membered monocyclic aromatic heterocyclic compound containing 1 to 4 heteroatoms selected from nitrogen atoms, sulfur atoms and oxygen atoms in addition to carbon atoms as ring-constituting atoms, and a compound containing at least 1 or more nitrogen atoms as ring-constituting atoms. Preferable examples of the "5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound" include, for example, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetrazole, triazine, etc. Among them, pyridine or imidazole is more preferable.

[0037] In this specification, "optionally substituted" means unsubstituted or having one or more substituents. Unless otherwise specified, the "substituent" includes (1) a halogen atom, (2) a nitro group, (3) a cyano group, (4) a C 1-30 alkyl group, (5) a haloC 1-6 alkyl group, (6) a C 3-8 cycloalkyl group, (7) a C 1-30 alkoxy group, (8) a haloC 1-6 alkoxy group, (9) a C 6-14 aryl group, etc. Among them, a halogen atom, a cyano group, a C 1-6 alkyl group, a haloC 1-6 alkyl group, a C 1-6 alkoxy group, a haloC 1-6 alkoxy group or a phenyl group is preferable, and a halogen atom (e.g., fluorine atom), a C 1-6 alkyl group (e.g., methyl, ethyl), a C 1-6 alkoxy group (e.g., methoxy, ethoxy) or a haloC 1-6 alkyl group (e.g., trifluoromethyl) is more preferable. When a plurality of substituents are present, each substituent may be the same or different. The above substituents may also be further substituted with one or more C 1-6 alkyl groups, C 1-6 alkoxy groups, halogen atoms, phenyl groups, etc.

[0038] In this specification, the "hydrocarbon solvent" means a solvent including an aromatic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent. Among them, an aliphatic hydrocarbon solvent is preferable from the viewpoints of odor and toxicity.

[0039] In this specification, examples of the "aromatic hydrocarbon solvent" include benzene, toluene, xylene, and the like.

[0040] In this specification, examples of the "aliphatic hydrocarbon solvent" include n - hexane, iso - hexane, heptane, octane, cyclohexane, methylcyclohexane, and mixed solvents thereof.

[0041] In this specification, "soluble in a hydrocarbon solvent" means that in a solution of the hydrocarbon solvent and the compound of the present invention at 25°C, the compound of the present invention dissolves at a concentration of 5% by weight or more to form a transparent and homogeneous solution.

[0042] (Compound of the present invention) Hereinafter, the compound of the present invention will be described.

[0043] The compound of the present invention has the following formula (1):

[0044] [Chemical formula]

[0045] [In the formula, R 1 , R 2 , R 3 and R 4 each independently represent one or more aryl groups substituted with fluorine atoms or fluoro - C 1-4 alkyl groups, 6-14 and [A + -H] represents a cation in which the ring nitrogen atom of a 5 - or 6 - membered monocyclic nitrogen - containing aromatic heterocyclic compound having 25 or more carbon atoms, substituted with the same or different two or more C 1-30 alkyl groups or C 1-30 alkoxy groups, is protonated.] It is a compound represented by

[0046] Preferred embodiments of A will be described below. As A, two identical or different C9-30 An alkyl group or C 9-30 A 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound substituted with an alkoxy group (e.g., pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetrazole, triazine, etc.) is preferred, and two same or different, C 14-30 An alkyl group or C 14-30 Pyridine or imidazole substituted with an alkoxy group is more preferred. Also, the total number of carbon atoms of A is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more.

[0047] Preferred specific examples of A include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecyl-5-octadecylpyridine, 2-nonadecyl-4-octadecyloxypyridine, 2-nonadecyl-6-octadecyloxypyridine, 4-nonadecyl-1-octadecylimidazole, 5-nonadecyl-1-octadecylimidazole, 2-nonadecyl-1-octadecylimidazole, etc.

[0048] (Method for producing (A (a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound having 25 or more carbon atoms substituted with two or more same or different alkyl groups or C 1-30 An alkyl group or C 1-30 An alkoxy group)) Said A is represented by the following formula:

[0049]

Chemical formula

[0050] (In the formula, the formula:

[0051]

Chemical formula

[0052] The group represented by is a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic group, X' represents a halogen atom, and R 5 represents an optionally substituted C 1-30 alkyl group, and n1 represents an integer of 2 or more. As shown by (), in a solvent that does not affect the reaction, in the presence of a base, the phosphonium salt (R 5 -CH2PPh3X') is reacted with the compound (a1) to obtain the compound (a2) (Step 1), and A can be produced by the reaction with a reducing agent (Step 2).

[0053] In the above Step 1, examples of the base used include sodium hydride, potassium carbonate, potassium tert-butoxide, etc. The usage amount of the base is 1 to 2 moles (preferably 1 to 1.2 moles) relative to the equivalent amount (1 mole) of the formyl group of the compound (a1). The usage amount of the phosphonium salt (R 5 -CH2PPh3X') is also 1 to 2 moles (preferably 1 to 1.2 moles) relative to the equivalent amount (1 mole) of the formyl group of the compound (a1). The reaction solvent for Step 1 is not particularly limited, but for example, ether solvents such as tetrahydrofuran and diethoxyethane, aromatic hydrocarbon solvents such as toluene, aliphatic hydrocarbon solvents such as n-hexane, dimethylformamide, dimethyl sulfoxide, etc. are preferred. The reaction temperature for Step 1 is preferably from room temperature to 180 °C. The reaction time for Step 1 is usually from 0.5 hour to 48 hours.

[0054] In the above Step 2, as the reducing agent, for example, hydrogen, ammonium formate, ammonium chloride, etc. can be used in the presence of a metal catalyst. As the metal catalyst, transition metal catalysts such as Pd / C and Pt / C are preferred. The usage amount of the metal catalyst is 0.001 to 1.0 mole (preferably 0.01 to 0.5 mole) relative to the equivalent amount (1 mole) of the double bond of the compound (a2). The reaction solvent for Step 2 is not particularly limited, but for example, n-hexane, toluene, tetrahydrofuran, ethanol, etc. are preferred, and a mixed solvent thereof may also be used. For the reduction reaction in Step 2, conditions such as normal pressure and medium pressure can be appropriately selected according to the progress of the reaction. The reaction temperature in Step 2 is preferably from room temperature to 180 °C. The reaction time in Step 2 is usually from 1 hour to 72 hours.

[0055] Preferred embodiments of the compound represented by the formula (1) (hereinafter also referred to as "compound (1)") will be described below.

[0056] Hereinafter, each group of compound (1) will be described.

[0057] R 1 、R 2 、R 3 and R 4 are preferably, each independently, a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group or 9-phenanthryl group substituted with one or more fluorine atoms or fluoro C 1-4 alkyl groups (e.g., trifluoromethyl group), more preferably, each independently, a phenyl group, 1-naphthyl group or 2-naphthyl group substituted with one or more fluorine atoms or trifluoromethyl groups, and particularly preferably, R 1 、R 2 、R 3 and R 4 are all the same, and are a pentafluorophenyl group, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group.

[0058] The preferred embodiment of A in [A-H] + , which is the cation derived from A, is the same as described above.

[0059] Examples of suitable compound (1) include the following compounds.

[0060] [Compound (1-1)] In the above formula (1), R 1 、R 2 、R 3 and R 4 are each independently a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group, or 9-phenanthryl group substituted with one or more fluorine atoms or fluorinated C 1-4 alkyl group (e.g., trifluoromethyl group), A is one or more of the same or different 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compounds (e.g., pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetrazole, triazine, etc.) substituted with a C 9-30 alkyl group or a C 9-30 alkoxy group, and the total number of carbon atoms is 25 or more (preferably 30 or more), Compound (1).

[0061] [Compound (1-2)] In the above formula (1), R 1 、R 2 、R 3 and R 4 are each independently a phenyl group, 1-naphthyl group or 2-naphthyl group substituted with one or more fluorine atoms or trifluoromethyl groups, A is one or two of the same or different C 14-30 alkyl groups or a C 14-30A pyridine or imidazole substituted with an alkoxy group (preferably 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecyl-5-octadecylpyridine, 2-nonadecyl-4-octadecyloxypyridine, 2-nonadecyl-6-octadecyloxypyridine, 4-nonadecyl-1-octadecylimidazole, 5-nonadecyl-1-octadecylimidazole, or 2-nonadecyl-1-octadecylimidazole), and Compound (1) having a total carbon number of 35 or more.

[0062] [Compound (1-3)] In the above formula (1) R 1 、R 2 、R 3 and R 4 are all the same pentafluorophenyl group, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group (preferably pentafluorophenyl group), A is two identical or different C 14-30 alkyl group or C 14-30 pyridine substituted with an alkoxy group (preferably 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecyl-5-octadecylpyridine, 2-nonadecyl-4-octadecyloxypyridine or 2-nonadecyl-6-octadecyloxypyridine), and Compound (1) having a total carbon number of 35 or more.

[0063] Preferable specific examples of the compound (1) include, for example, 2,6-dinonadecylpyridinium tetrakis(pentafluorophenyl)borate, 2-nonadecyl-5-octadecyloxypyridinium tetrakis(pentafluorophenyl)borate, 4-nonadecyl-1-octadecylimidazolium tetrakis(pentafluorophenyl)borate, 5-nonadecyl-1-octadecylimidazolium tetrakis(pentafluorophenyl)borate, 2-nonadecyl-1-octadecylimidazolium tetrakis(pentafluorophenyl)borate, and the like.

[0064] The compound of the present invention is soluble in a hydrocarbon solvent at room temperature (15 to 30 °C). Further, while a conventionally known borate type cocatalyst is insoluble in an aliphatic hydrocarbon solvent such as n-hexane, the compound of the present invention is soluble in an aliphatic hydrocarbon solvent, and thus is useful as a cocatalyst for a homogeneous polymerization reaction of an olefin or a diene.

[0065] (Method for producing the compound of the present invention) Hereinafter, the method for producing the compound of the present invention (hereinafter, also referred to as "the production method of the present invention") will be described.

[0066] The compound of the present invention preferably does not contain a borohydride compound represented by the following formula (3) (for example, tetrakis(pentafluorophenyl)borate hydride) or a metal salt of a tetra-substituted borate compound (for example, lithium tetrakis(pentafluorophenyl)borate), which can form a complex with an ether compound having 7 or less carbon atoms in total and serve as a catalyst poison. Further, the composition of the present invention preferably does not contain an ether compound having 7 or less carbon atoms in total, which can serve as a catalyst poison. Not containing an ether compound having 7 or less carbon atoms in total means 1 As a result of 1H-NMR analysis, it means that an ether compound having 7 or less carbon atoms in total is not detected.

[0067] The production method of the present invention is represented by the following formula (3):

[0068] [Chemical formula]

[0069] [wherein R 1 , R 2 , R 3 and R 4 are as defined above.] A process comprising reacting a borohydride compound represented by (hereinafter also referred to as "compound (3)") with the above A, and using an equimolar amount (1 to 1.01 mol, preferably 1 mol) of A per 1 mol of compound (3).

[0070] In this production method, examples of the compound (3) used as a raw material include known compounds such as tetrakis(pentafluorophenyl)borate hydride, tetrakis(nonafluoro[1,1'-biphenyl]-4-yl)borate hydride, tetrakis(heptafluoro-2-naphthyl)borate hydride, [3,5-bis(trifluoromethyl)phenyl]borate hydride, and the like.

[0071] The production method of compound (3) is not particularly limited. For example, formula (4):

[0072] [Chemical formula]

[0073] [wherein R 1 , R 2 , R 3 and R 4 each independently represents an aryl group having one or more fluorine atoms or a C 1-4 aryl group substituted with a fluoro C 6-14 alkyl group, M represents an alkali metal such as lithium, potassium, sodium, or an alkaline earth metal such as calcium, magnesium, barium, and n represents 1 or 2.]. Examples of the method include treating the compound represented by (hereinafter also referred to as "compound (4)") with a protic acid.

[0074] As the compound (4) used in the production of the compound (3), commercially available products or purified products may be used, or those prepared by a method known per se (see, for example, Angew. Chem. Int. Ed., 2009, 48(40), 7444 - 7447) may be used.

[0075] The solvent used in the production of the compound (3) is not particularly limited, but it is desirable to use ether solvents such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, diisopropyl ether, halogen solvents such as dichloromethane, chloroform, aromatic hydrocarbon solvents such as toluene, benzene, and aliphatic hydrocarbon solvents such as n-hexane, isohexane, heptane, octane, cyclohexane, methylcyclohexane. Also, these solvents may be used alone or in combination.

[0076] Also, the protonic acid used when treating the compound (4) is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, etc.

[0077] The amount of the protonic acid used in the production of the compound (3) is desirably an equimolar amount (1 to 1.01 mol, preferably 1 mol) relative to 1 mol of the compound (4). When using 1 mol or more of the protonic acid, it is preferable to wash the organic phase with water until the pH of the aqueous phase after washing is 3 or more so that the protonic acid used in the organic phase after treatment does not remain. When the pH of the aqueous phase is less than 3, there is a concern that the protonate of the protonic acid used in the organic phase remains, and in the subsequent reaction with A, the protonate of A is formed and remains in the composition of the present invention, becoming a catalyst poison during polymerization.

[0078] In this production method, the solution of the compound (3) prepared as described above can be directly used for the reaction with A.

[0079] As A used in the production method of the present invention, there may be mentioned 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compounds having 25 or more carbon atoms in total (preferably 30 or more, more preferably 35 or more) as described above. Specific examples of A include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecyl-5-octadecylpyridine, 2-nonadecyl-4-octadecyloxypyridine, 2-nonadecyl-6-octadecyloxypyridine, 4-nonadecyl-1-octadecylimidazole, 5-nonadecyl-1-octadecylimidazole, 2-nonadecyl-1-octadecylimidazole and the like.

[0080] Among them, compound (3) and C 9-30 an alkyl group (preferably C 14-30 alkyl group) or C 9-30 an alkoxy group (preferably C 14-30 alkoxy group), having two or more (preferably two) of them, and obtained by reacting with A having 25 or more carbon atoms in total, compound (1) becomes soluble in a hydrocarbon solvent.

[0081] In the production method of the present invention, the reaction temperature and time are not particularly limited, but the reaction temperature is usually 0 ° C to 40 ° C, preferably 10 to 35 ° C, more preferably room temperature (15 to 30 ° C), and the time is 10 minutes or more.

[0082] After completion of the reaction between compound (3) and the above A, the reaction solution is dehydrated with a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and then the solvent is removed to obtain compound (1).

[0083] Also, as another method, after completion of the reaction between compound (3) and the above A, a part of the reaction solvent is distilled off, or solvent dilution and solvent distillation (solvent substitution) are carried out once or a plurality of times to obtain a solution of compound (1).

[0084] A preferred embodiment of the above compound (3) conforms to a preferred embodiment of the anion moiety in the above compound (1) (the anion moieties of compounds (1-1) to (1-3)).

[0085] As yet another alternative method, a salt of the above A and a protonic acid (for example, hydrochloride of A) is prepared in advance, and an equimolar amount of the salt and compound (4) are mixed in a solvent and stirred, whereby a solution of compound (1) can also be obtained.

[0086] In the alternative method, the types of the protonic acid and the solvent, the reaction temperature, the reaction time, etc. are in accordance with the above-described production method of the present invention.

[0087] Examples of suitable compound (4) include the following compounds. [Compound (4-1)] In the above formula (4), R 1 , R 2 , R 3 and R 4 are each independently a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3-phenanthryl group or 9-phenanthryl group substituted with one or more fluorine atoms or fluoro C 1-4 alkyl groups (e.g., trifluoromethyl group), M is lithium, sodium, potassium, calcium, magnesium or barium, and n is 1 or 2, Compound (4).

[0088] [Compound (4-2)] In the above formula (4), R 1 , R 2 , R 3 and R 4 are each independently a phenyl group, 1-naphthyl group or 2-naphthyl group substituted with one or more fluorine atoms or trifluoromethyl groups, M is lithium, sodium or potassium, and n is 1, Compound (4).

[0089] [Compound (4-3)] In the above formula (4), R 1 , R 2 , R 3 and R 4 are all the same and are a pentafluorophenyl group, a 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenylyl) group, a 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or a 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group, M is lithium or sodium, and n is 1, Compound (4).

[0090] Preferred specific examples of Compound (4) include, for example, lithium tetrakis(pentafluorophenyl)borate, sodium tetrakis(pentafluorophenyl)borate, lithium tetrakis(nonafluoro[1,1'-biphenyl]-4-yl)borate, lithium tetrakis(heptafluoro-2-naphthyl)borate, lithium [3,5-bis(trifluoromethyl)phenyl]borate, sodium [3,5-bis(trifluoromethyl)phenyl]borate, lithium tetrakis(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borate, lithium tetrakis(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borate, sodium tetrakis(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borate, sodium tetrakis(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borate and other known compounds.

[0091] The compound of the present invention is soluble in a hydrocarbon solvent and does not contain a compound that can be a catalyst poison such as an amine compound having high basicity and nucleophilicity, its protonate, or an ether compound having 7 or less carbon atoms in total. Therefore, it is useful as a cocatalyst for the polymerization of olefins and dienes.

[0092] The present invention encompasses a method for producing a polymer, which includes polymerizing at least one monomer selected from the group consisting of olefins and dienes using the compound of the present invention as a cocatalyst.

[0093] The production of the polymer using the compound of the present invention as a cocatalyst can be specifically carried out, for example, according to the method described in the test examples described below.

Examples

[0094] The present invention will be specifically described by the following production examples and examples, but the present invention is not limited only to these production examples and examples. % indicates mol / mol% for the yield, and for others, it indicates weight% unless otherwise specified. Also, room temperature indicates a temperature of 15°C to 30°C unless otherwise specified.

[0095] In addition, the following equipment was used for analysis. 1 H-NMR and 19 F-NMR: 400YH manufactured by JEOL Ltd. Also, the solvents and reagents used in the following examples were purchased from vendors such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Corporation, Junsei Chemical Co., Ltd., Kanto Chemical Co., Ltd., Combi-Blocks, etc. when not specifically stated. The deuterated solvents used for NMR measurement were purchased from Cambridge Isotope Laboratories.

[0096] [Production Example 1] Synthesis of 2,6-bis(nonadec-1-yl)pyridine To a mixture of pyridine-2,6-dicarbaldehyde (1.0 g, 7.4 mmol), octadecyltriphenylphosphonium bromide (10 g, 17 mmol) and tetrahydrofuran (100 mL), potassium tert-butoxide (2.0 g, 18 mmol) was added at room temperature. The mixture was stirred at 60 °C for 2 hours and then allowed to cool to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was suspended in diethyl ether, the insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2 to 90 / 10) to obtain 2,6-bis(nonadec-1-enyl)pyridine (E / Z mixture; 3.9 g, 86%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.20 - 1.48 (60H, m), 2.56 - 2.62 (4H, m), 5.82 - 5.89(1H, m), 6.42 - 6.49 (2H, m), 7.04 (2H, d), 7.26 - 7.35 (1H, m), 7.53 - 7.57 (1H, m).

[0097] [Production Example 2] Synthesis of 2,6-di(nonyladecyl)pyridine A mixture of 2,6-bis(nonadec-1-enyl)pyridine (E / Z mixture; 3.5 g, 5.8 mmol) obtained in Production Example 1, 10% Pd / C (50% water-containing; 0.70 g) and tetrahydrofuran (100 mL) was stirred at room temperature and normal pressure for 15 hours under a hydrogen atmosphere. After the mixture was filtered, the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to obtain 2,6-di(nonyladecyl)pyridine (3.0 g, 85%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.17 - 1.40 (64H, m), 1.65 - 1.70 (4H, m), 2.72 - 2.76 (4H, m), 6.93 (2H, d), 7.48 (1H, t).

[0098] [Production Example 3] Synthesis of 2,6 - Di(nonadecyl)pyridine Hydrochloride To a solution of 2,6 - di(nonadecyl)pyridine (3.0 g, 4.9 mmol) obtained in Production Example 2 in n - hexane (30 mL), 1 M hydrogen chloride - diethyl ether solution (10 mL) was added at room temperature, and the mixture was stirred for 1 hour. The resulting precipitate was collected by filtration, washed with n - hexane, and dried under reduced pressure to obtain 2,6 - di(nonadecyl)pyridine hydrochloride (3.0 g, 94%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.24 - 1.45 (64H, m), 1.79 - 1.87 (4H, m), 3.32 (4H, br), 7.41 (2H, d), 8.08 (1H, br).

[0099] [Example 1] 2,6 - Di(nonadecyl)pyridinium Tetrakis(pentafluorophenyl)borate 2,6 - Di(nonadecyl)pyridine hydrochloride (0.50 g, 0.77 mmol) obtained in Production Example 3 and a diethyl ether complex of lithium tetrakis(pentafluorophenyl)borate (0.59 g, 0.78 mmol) were suspended in dichloromethane (20 mL), and then stirred at room temperature for 1 hour. The resulting suspension was filtered, and the filtrate was concentrated under reduced pressure at 50 °C to obtain 2,6 - di(nonadecyl)pyridinium tetrakis(pentafluorophenyl)borate (0.99 g, 99%). 1 H NMR (CDCl3) δ: 0.85 - 0.89 (6H, m), 1.23 - 1.35 (64H, m), 1.72 - 1.76 (4H, m), 2.94 - 2.98 (4H, t), 7.57 (2H, d), 8.27 (1H, dd); 19 F NMR (CDCl3) δ: - 133.3 (8F, t), - 163.2 (4F, t), - 167.7 (8F, t).

[0100] It was confirmed that the compound obtained in Example 1 was dissolved in methylcyclohexane at a concentration of 10% by weight.

[0101] [Production Example 4] Synthesis of 2-(nonadec-1-yl)-5-octadecyloxypyridine To a mixture of 5-octadecyloxypyridine-2-carbaldehyde (2.0 g, 5.3 mmol), octadecyltriphenylphosphonium bromide (7.0 g, 12 mmol) and tetrahydrofuran (100 mL), potassium tert-butoxide (1.4 g, 12 mmol) was added at room temperature. The mixture was stirred at 60 °C for 2 hours and allowed to cool to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was suspended in diethyl ether, insolubles were filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2 - 90 / 10) to obtain 2-(nonadec-1-yl)-5-octadecyloxypyridine (E / Z mixture; 3.1 g, 95%). 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.24 - 1.50 (60H, m), 1.76 - 1.80 (2H, m), 2.48 - 2.54 (2H, m), 3.95 - 4.00 (2H, m), 7.71 - 7.78 (1H, m), 6.36 - 6.40 (1H, m), 7.13 - 7.18 (2H, m), 8.2 - 8.27 (1H, m).

[0102] [Production Example 5] Synthesis of 2-nonadecyl-5-octadecyloxypyridine A mixture of 2-(nonadec-1-enyl)-5-octadecyloxypyridine (E / Z mixture; 2.5 g, 4.1 mmol) obtained in Production Example 4, 10% Pd / C (50% water-containing; 0.70 g), n-hexane (100 mL) and tetrahydrofuran (100 mL) was stirred under a hydrogen atmosphere at room temperature and normal pressure for 15 hours. After filtering the reaction mixture, the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to obtain 2-nonadecyl-5-octadecyloxypyridine (1.0 g, 40%). 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.17 - 1.40 (64H, m), 1.42 - 1.76 (4H, m), 2.67 - 2.72 (2H, m), 3.95 (1H, t), 7.02 (2H, d), 7.10 (2H, dd), 8.19 (1H, d).

[0103] [Production Example 6] Synthesis of 2-nonadecyl-5-octadecyloxypyridine hydrochloride To a mixture of 2-nonadecyl-5-octadecyloxypyridine (1.0 g, 1.63 mmol) obtained in Production Example 5 and n-hexane (100 mL) was added 1.0 M hydrogen chloride-diethyl ether (10 mL), and the mixture was stirred for 1 hour. By distilling off the solvent under reduced pressure, the title compound (0.98 g, 93%) was obtained. 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.24 - 1.45 (62H, m), 1.78 - 1.83 (4H, m), 3.14 (2H, t), 4.96 (2H, t), 7.50 (1H, d), 7.73 - 7.76 (1H, m), 8.20 (1H, d).

[0104] [Example 2] Synthesis of 2-nonadecyl-5-octadecyloxypyridinium tetrakis(pentafluorophenyl)borate 2-Nonadecyl-5-octadecyloxypyridine hydrochloride (0.25 g, 0.38 mmol) and lithium tetrakis(pentafluorophenyl)borate diethyl ether complex (0.29 g, 0.38 mmol) obtained in Production Example 6 were suspended in cyclohexane (50 mL), and then stirred at room temperature for 1 hour. Brine was added, and after washing the organic phase, it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By drying under reduced pressure at 45 °C, the title compound (0.45 g, 90%) was obtained. 1 H NMR (CDCl3) δ: 0.86 - 0.90 (6H, m), 2.00 - 1.44 (62H, m), 1.70 - 1.86 (4H, m), 2.91 (2H, t), 4.04 (2H, t), 7.66 (1H, d), 7.83 (1H, d), 7.93 (1H, dd); 19 F NMR (CDCl3) δ: -134.0 (8F, d), -163.4 (4F, t), -167.5 (8F, t).

[0105] It was confirmed that the compound obtained in Example 2 was dissolved in methylcyclohexane at a concentration of 10% by weight.

[0106] [Production Example 7] Synthesis of 1-octadecylimidazole-2-carbaldehyde A mixture of 1H-imidazole-2-carbaldehyde (2.0 g, 21 mmol), 1-bromooctadecane (7.5 g, 22 mmol), potassium carbonate (4.5 g, 33 mmol) and N,N-dimethylformamide was stirred at room temperature for 15 hours. The mixture was poured into water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (n-hexane - ethyl acetate = 98 / 2 - 90 / 10) to obtain 1-octadecylimidazole-2-carbaldehyde (6.45 g, 89%). 11H NMR (CDCl3) δ: 0.88 (3H, t), 1.24 - 1.30 (34H, m), 1.75 - 1.79 (2H, m), 4.36 - 4.40 (2H, m), 7.15 (1H, s), 7.29 (1H, d), 9.81 (1H, s).

[0107] [Production Example 8] Synthesis of 2-(nonadec-1-yl)-1-octadecylimidazole To a mixture of 1-octadecylimidazole-2-carbaldehyde (5.0 g, 14 mmol) obtained in Production Example 7, octadecyltriphenylphosphonium bromide (10 g, 16.8 mmol), and tetrahydrofuran (50 mL), potassium tert-butoxide (2.0 g, 17.8 mmol) was added at room temperature. The mixture was stirred at 60 °C for 2 hours and then allowed to cool to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was suspended in diethyl ether, and the insoluble matter was filtered off. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2 - 90 / 10) to obtain 2-(nonadec-1-yl)-1-octadecylimidazole (E / Z mixture; 7.5 g, 89%). 1 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.11 - 1.73 (64H, m), 2.20 - 2.26 (2H, m), 3.85 - 3.90 (2H, m), 6.11 - 6.23 (1H, m), 6.67 - 6.74 (1H, m), 6.81 - 6.82 (1H, m), 6.98 - 7.09 (1H, m).

[0108] [Production Example 9] Synthesis of 2-nonadecyl-1-octadecylimidazole A mixture of 2-(nonadec-1-enyl)-1-octadecylimidazole (E / Z mixture; 1.5 g, 2.6 mmol) obtained in Production Example 8, 10% Pd / C (50% water-containing; 0.30 g), and tetrahydrofuran (100 mL) was stirred under a hydrogen atmosphere at room temperature and normal pressure for 15 hours. After the mixture was filtered, the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to obtain 2-nonadecyl-1-octadecylimidazole (1.0 g, 67%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25 - 1.75 (66H, m), 2.60 - 2.64 (2H, m), 3.79 - 3.82 (2H, m), 6.79 (1H, d), 6.93 (1H, d).

[0109] [Production Example 10] Synthesis of 2-nonadecyl-1-octadecylimidazole hydrochloride To a suspension of 2-nonadecyl-1-octadecylimidazole (0.88 g, 1.5 mmol) obtained in Production Example 9 and n-hexane (100 mL) was added a 1M hydrogen chloride-diethyl ether solution (10 mL) at room temperature, and the mixture was stirred for 1 hour. By distilling off the solvent of the obtained suspension under reduced pressure, 2-nonadecyl-1-octadecylimidazole hydrochloride (0.98 g, 100%) was obtained. 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25 - 1.40 (62H, m), 1.80 - 1.88 (4H, m), 3.02 - 3.07 (2H, t), 3.96 - 4.00 (2H, t), 6.97 (1H, d), 7.29 (1H, d).

[0110] [Example 3] Synthesis of 2-nonadecyl-1-octadecylimidazolium tetrakis(pentafluorophenyl)borate 2-Nonadecyl-1-octadecylimidazolium hydrochloride (0.98 g, 1.57 mmol) and lithium tetrakis(pentafluorophenyl)borate diethyl ether complex (1.19 g, 1.57 mmol) obtained in Production Example 10 were suspended in cyclohexane (30 mL), and then stirred at room temperature for 1 hour. Brine was added, and the organic phase was washed, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Drying under reduced pressure at 45 °C gave 2-nonadecyl-1-octadecylimidazolium tetrakis(pentafluorophenyl)borate (0.82 g, 94%). 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25 - 1.43 (62H, m), 1.66 - 1.82 (4H, m), 2.81 (2H, t), 3.94 (2H, t), 6.99 (1H, d), 7.03 (1H, d); 19 F NMR (CDCl3) δ: -133.9 (8F, t), -164.1 (4F, t), -167.9 (8F, t).

[0111] It was confirmed that the compound obtained in Example 3 was soluble in methylcyclohexane at a concentration of 10% by weight.

[0112] [Test Example] (Evaluation of Polymerization Performance) A general polymerization method using the compound or composition of the present invention as a cocatalyst is shown below.

[0113] In a glove box, 1-octene, triisobutylaluminum (TIBA, 0.55 M n-hexane solution), and a solvent (methylcyclohexane (MCH)) were added to a 100 mL autoclave to prepare a comonomer solution. A polymerization catalyst (dimethylsilylene(tert-butylamide)-(tetramethylcyclopentadienyl)-titanium(IV)-dichloride (CGC)), triisobutylaluminum (0.55 M n-hexane solution), and a solvent were added to prepare a catalyst solution with a predetermined concentration, which was then transferred to a Schlenk tube. A cocatalyst was dissolved in a solvent to prepare a cocatalyst solution with a predetermined concentration, which was then transferred to a Schlenk tube. During the reaction after mixing the comonomer solution, the catalyst solution, and the cocatalyst solution, the total amount of the solvent and the total amount of triisobutylaluminum were adjusted to be constant. After purging the inside of the autoclave with ethylene gas, the catalyst solution and the cocatalyst solution were sequentially added to the autoclave, and immediately, the ethylene pressure was adjusted to a predetermined pressure, and the mixture was stirred at a predetermined temperature (25 °C) for a predetermined time. After the reaction mixture was ice-cooled and the ethylene gas was removed, the mixture was poured into methanol (100 mL) containing hydrochloric acid (3 mL) and stirred at room temperature for 30 minutes. The precipitate was collected by filtration and dried under reduced pressure at 60 °C to obtain an ethylene-octene copolymer.

[0114] (Melting point measurement) Measurement by differential scanning calorimetry (DSC) was performed using a DSC6220 instrument (Seiko Instruments Inc.). The sample (polymer) was heated from 40 °C to 150 °C at a rate of 10 °C / min, and the melting point was measured.

[0115] The results of the polymerization reaction at 25 °C using various cocatalysts are shown in Table 1 below. As the cocatalyst for Comparative Example 1, N,N-dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate obtained by a method known per se (see, for example, U.S. Patent No. 6,121,185, etc.) was used.

[0116]

Table 1

[0117] According to Table 1, it was confirmed that both Examples 1 and 2 exhibited higher polymerization activity than Comparative Example 1.

Industrial Applicability

[0118] Since the compound of the present invention is soluble in a hydrocarbon solvent and does not act as a catalyst poison, it is useful as a cocatalyst for the polymerization of olefins and dienes.

[0119] This application is based on Japanese Patent Application No. 2020-209071 filed in Japan on December 17, 2020, the content of which is incorporated herein in its entirety.

Claims

1. The following formula (1): 【Chemical 1】 [In the formula, R １ , R ２ , R ３ and R ４ all represent a pentafluorophenyl group, [A ＋ -H] represents a cation in which the ring nitrogen atom of pyridine or imidazole having 25 or more carbon atoms, substituted with two identical or different C9-30 alkyl groups or C9-30 alkoxy groups, is protonated. ] A compound represented by the formula.

2. A cocatalyst for the polymerization of at least one monomer selected from the group consisting of olefins and dienes, comprising the compound according to Claim 1.

3. A method for producing a polymer, comprising polymerizing at least one monomer selected from the group consisting of olefins and dienes using the compound according to Claim 1 as a cocatalyst.

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