Ammonium fluoroalkyl borate compound and method for producing the same

Abstract

An object of the present invention is to provide a compound useful as a cocatalyst for use in the polymerization reactions of olefins, dienes and acetylenes. According to the present invention, there can be provided a fluorinated alkylammonium borate compound represented by the following formula (1) [the definitions of the respective symbols in the formula are as described in the specification.] which is useful and highly active as a cocatalyst for use in the polymerization reactions of olefins, dienes and acetylenes, a composition containing the same, and a method for producing them. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a fluorine-containing alkylammonium borate compound useful as a co-catalyst for the polymerization of olefins, dienes and acetylene, a composition containing the same, and a method for producing the same. Background Art

[0002] Conventionally, many reports have used non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for the polymerization of olefins, dienes, and acetylene. Cocatalysts used to stabilize the cationic active species of these metal complex catalysts include aluminum alkyls, aluminoxanes such as methylaluminoxane (MAO), Bronsted acid salts such as ammonium borate, and Lewis acid salts such as triphenylborate (Non-Patent Document 1).

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

[0004] Known examples of the aforementioned Bronsted acid salts include nitrogen-containing Bronsted acid salts (ammonium borates) such as dimethylanilinium tetrakis(pentafluorophenyl)borate, tri-n-butylammonium tetrakis(pentafluorophenyl)borate, and methylpyrrolidinium tetrakis(pentafluorophenyl)borate (Patent Document 2). In catalyst activation reactions using these ammonium borates, neutral amine compounds are generated by losing protons during the protonation stage. These neutral amine compounds may interact with the cationic active species of the metal complex catalyst, potentially adversely affecting the polymerization reaction.

[0005] In order to reduce the basicity of the neutral amine compound generated in the catalyst activation reaction, N-(pentafluorophenyl)pyrrolidinium tetrakis(pentafluorophenyl)borate and the like have been proposed as co-catalysts (Patent Document 3).

[0006] Prior art literature

[0007] Non-patent literature

[0008] Non-patent document 1: Chem. Rev. 2000, 100, 1391-1434

[0009] Patent Literature

[0010] Patent Document 1: U.S. Patent No. 5,132,380

[0011] Patent Document 2: International Publication No. 2010 / 014344

[0012] Patent Document 3: International Publication No. 2001 / 042249 Summary of the invention

[0013] Problems to be solved by the invention

[0014] In view of these prior arts, the present inventors have provided a fluorine-containing alkyl ammonium borate compound as a cocatalyst for use in the polymerization reaction of olefins, dienes and acetylene using a metal complex catalyst, which exhibits higher polymerization activity than the prior arts, a composition containing the same, and an industrial production method thereof.

[0015] Solutions for solving problems

[0016] The present inventors conducted intensive research and were the first to discover that the compound represented by the following formula (1) (hereinafter also referred to as "the compound of the present invention") exhibits high metal complex catalyst activation ability in the polymerization reaction of olefins, dienes and acetylene and is useful as a co-catalyst, thereby completing the present invention.

[0017]

[0018] [Where,

[0019] R 1 , R 2 , R 3 and R 4 Each independently represents a fluorine atom or a fluorinated C 1-4 Alkyl substituted C 6-14 Aryl,

[0020] R 5 represents C substituted with one or more substituents 1-30 Alkyl, the substituent is selected from C 6-14 A group consisting of an aromatic group and a fluorine atom,

[0021] R 6 and R 7 Each independently represents an optionally substituted C 1-30 Alkyl, optionally substituted C 3-15 Cycloalkyl or optionally substituted C 6-14 Aryl, or

[0022] R 6 and R 7The mutual bonds together with the nitrogen atoms to which they are bonded form an optionally substituted cyclic group.

[0023] n represents 1, and

[0024] m represents 1 or 2.

[0025] That is, the present invention is as follows.

[0026] [1] A compound represented by the following formula (1).

[0027]

[0028] [In the formula,

[0029] R 1 、R 2 、R 3 and R 4 each independently represent a C 1-4 aryl substituted by one or more fluorine atoms or one or more fluorinated C 6-14 alkyl groups,

[0030] R 5 represents a C 1-30 alkyl group substituted by one or more substituents selected from the group consisting of a C 6-14 aryl group substituted by one or more fluorine atoms and fluorine atoms,

[0031] R 6 and R 7 each independently represent an optionally substituted C 1-30 alkyl group, an optionally substituted C 3-15 cycloalkyl group or an optionally substituted C 6-14 aryl group; or

[0032] R 6 and R 7 mutually bond together with the nitrogen atom to which they are bonded to form an optionally substituted cyclic group,

[0033] n represents 1, and

[0034] m represents 1 or 2.

[0035] [2] The compound according to the foregoing [1], wherein R 1 、R 2 、R 3 and R 4 are each independently phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 9-phenanthryl or 3-phenanthryl, each substituted by one or more fluorine atoms or one or more fluorinated C 1-4 alkyl groups.

[0036] [3] The compound according to [1], wherein R 1 , R 2 , R 3 and R 4 All are pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl.

[0037] [4] The compound according to any one of [1] to [3], wherein R 5 C substituted by phenyl or naphthyl 1-6 Alkyl, or fluorinated C 1-6 The alkyl group, the phenyl group or the naphthyl group are each substituted with one or more fluorine atoms.

[0038] [5] The compound according to any one of [1] to [4], wherein R 6 and R 7 Each is independently selected from (1) C optionally substituted by a halogen atom 6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 Alkyl; or

[0039] Optionally selected from (1) halogen atoms, (2) C 1-30 Alkyl, (3)C 1-30 Alkoxy, (4) halogenated C 1-30 Alkyl and (5) halogenated C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 3-8 Cycloalkyl.

[0040] [6] The compound according to any one of [1] to [4], wherein R 6 and R 7 They are bonded to each other and, together with the nitrogen atom to which they are bonded, form an optionally substituted cyclic group derived from a 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group.

[0041] [7] The compound according to any one of [1] to [4], wherein R 5 Fluorinated C 1-6 alkyl, and

[0042] R 6 and R 7 Each is independently selected from (1) C optionally substituted by a halogen atom 6-14 Aryl group, (2) halogen atom and (3) C1-30 C substituted by a substituent in the group consisting of alkoxy 1-30 alkyl group.

[0043] [8] The compound according to any one of the foregoing [1] to [7], wherein both n and m are 1.

[0044] [9] The compound according to any one of the foregoing [1] to [8], wherein R 5 , R 6 and R 7 have a total carbon atom number of 25 or more.

[0045]

[10] A composition (hereinafter also referred to as "the composition of the present invention"), which contains the compound according to any one of the foregoing [1] to [9] and the compound represented by the following formula (2).

[0046]

[0047] [In the formula,

[0048] R and R' each independently represent an optionally substituted C 1-30 alkyl group, an optionally substituted C 3-15 cycloalkyl group or an optionally substituted C 6-14 aryl group. ]

[0049]

[11] The composition according to the foregoing

[10] , wherein R and R' are each independently an optionally substituted C 1-30 alkyl group.

[0050]

[12] The composition according to the foregoing

[10] or

[11] , wherein, relative to 1 mole of the compound represented by the foregoing formula (1), the content of the compound represented by the foregoing formula (2) is in the range of 0.01 to 10 moles.

[0051]

[13] The composition according to the foregoing

[10] or

[11] , wherein, relative to 1 mole of the compound represented by the foregoing formula (1), the content of the compound represented by the foregoing formula (2) is in the range of 0.1 to 3 moles.

[0052]

[14] A composition, which contains the compound according to any one of the foregoing [1] to [9] and the compound represented by the following formula (3) (wherein, in this composition, the compound represented by the formula (3) is an amine compound obtained by deprotonating the cation constituting the formula (1) described in the foregoing [1]).

[0053]

[0054] [In the formula, R 5 , R 6 and R 7Means the same as above.]

[0055]

[15] The composition according to

[14] , wherein the content of the compound represented by the formula (3) is in the range of 0.01 to 10 mol per 1 mol of the compound represented by the formula (1).

[0056]

[16] The composition according to

[14] , wherein the content of the compound represented by the formula (3) is in the range of 0.5 to 3 mol per 1 mol of the compound represented by the formula (1).

[0057]

[17] The composition according to any one of

[14] to

[16] , further comprising a compound represented by the following formula (2).

[0058]

[0059] [Where,

[0060] R and R' each independently represent an optionally substituted C 1-30 Alkyl, optionally substituted C 3-15 Cycloalkyl or optionally substituted C 6-14 Aryl.]

[0061]

[18] A cocatalyst for the polymerization of at least one monomer selected from the group consisting of olefins, dienes, and acetylene, the cocatalyst comprising the compound described in any one of [1] to [9] above or the composition described in any one of

[10] to

[17] above.

[0062]

[19] A method for producing a polymer, comprising: using the compound described in any one of [1] to [9] or the composition described in any one of

[10] to

[17] as a co-catalyst to polymerize at least one monomer selected from the group consisting of olefins, dienes and acetylene.

[0063]

[20] A method for producing a compound represented by the following formula (1):

[0064]

[0065] [Where,

[0066] R 1 , R 2 , R 3 and R 4 Each independently represents a fluorine atom or a fluorinated C 1-4 Alkyl substituted C 6-14 Aryl,

[0067] R 5represents a C selected from (1) substituted with one or more fluorine atoms 6-14 C substituted with one or more substituents from the group consisting of an aryl group and (2) a fluorine atom 1-30 alkyl,

[0068] R 6 and R 7 Each independently represents an optionally substituted C 1-30 Alkyl, optionally substituted C 3-15 Cycloalkyl or optionally substituted C 6-14 Aryl, or

[0069] R 6 and R 7 are bonded to each other and to the nitrogen atom to which they are bonded to form an optionally substituted cyclic group,

[0070] n represents 1, and

[0071] m represents 1 or 2.]

[0072] The production method is characterized in that it includes a step of reacting a compound represented by the following formula (4) with a compound represented by the following formula (3) in the presence of a protonic acid.

[0073]

[0074] [Where,

[0075] R 1 , R 2 , R 3 and R 4 Means the same as above,

[0076] M p+ represents an alkali metal ion or an alkaline earth metal ion, and

[0077] p represents 1 or 2.]

[0078]

[0079] [R in the formula 5 , R 6 and R 7 Means the same as above.]

[0080] Effects of the Invention

[0081] The present invention provides a fluorine-containing alkylammonium borate compound that exhibits high metal complex catalyst activation ability in the polymerization reaction of olefins, dienes, and acetylene and is useful as a cocatalyst; a composition containing the same; and an industrial production method thereof. DETAILED DESCRIPTION

[0082] The definitions of the terms and symbols used in this specification are explained below.

[0083] In this specification, a "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0084] In the present specification, the "alkyl group" refers to a linear or branched alkyl group having 1 or more carbon atoms.

[0085] In this manual, "C 1-30 The term "alkyl (group)" refers to a linear or branched alkyl group having 1 to 30 carbon atoms, and examples thereof include 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, and triacontyl.

[0086] In this manual, "C 1-18 The term "alkyl (group)" refers to a linear or branched alkyl group having 1 to 18 carbon atoms, and examples thereof include 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, and octadecyl.

[0087] In this manual, "C 1-6 The term "alkyl (group)" refers to a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include 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, and 2-ethylbutyl. Among them, C 1-4 alkyl.

[0088] In this specification, "halogenated C 1-30 Alkyl (group)" refers to the aforementioned "C 1-30"alkyl" group in which one or more hydrogen atoms are substituted by halogen atoms. Specifically, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, 6,6,6-trifluorohexyl, etc. can be cited. Among them, the aforementioned "halogenated C 1-30 The halogen atom in the "alkyl (group)" is preferably a fluorine atom, preferably a C 1-30 Alkyl, i.e. "fluoro-C 1-30 "alkyl (group)".

[0089] In this specification, "halogenated C 1-6 Alkyl (group)" refers to the aforementioned "C 1-6 "alkyl" group in which one or more hydrogen atoms are substituted by halogen atoms. Specifically, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, 6,6,6-trifluorohexyl, etc. are mentioned. Among them, the aforementioned "halogenated C 1-6 "Fluoro-C" in which the halogen atom in the alkyl group is a fluorine atom 1-6 "alkyl (group)".

[0090] As "Fluoro-C 1-6 Specific examples of the "alkyl (group)" include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 2,2-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 4,4,4-trifluorobutyl, 2,2-difluoropentyl, 5,5,5-trifluoropentyl, 2,2-difluorohexyl, and 6,6,6-trifluorohexyl. Among them, as R 5 The definition of fluorinated C 1-6Specific examples of the alkyl (group), preferably 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc., are fluorinated C having fluorine atoms at the β-position and / or γ-position 1-6 alkyl (group), more preferably 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc., are fluorinated C having a fluorine atom at the β-position 1-4 alkyl (group), further preferably 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc., are fluorinated C having a fluorine atom at the β-position and having more than 3 fluorine atoms 2-4 alkyl (group).

[0091] Regarding as R 1 、R 2 、R 3 and R 4 in the C 6-14 aryl substituents, or R 6 and R 7 are bonded to each other and form a cyclic group together with the nitrogen atom to which they are bonded. Specific examples of the "fluorinated C 1-4 alkyl (group)" of the substituent include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, 1,1,2,2-tetrafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, nonafluorobutyl, 1,1,2,2-tetrafluorobutyl, 2,2-difluorobutyl, 1,1-difluorobutyl, 4,4,4-trifluorobutyl, etc. Among them, trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl, 1,1-difluoropropyl, heptafluoropropyl, 1,1-difluorobutyl, nonafluorobutyl are preferred, and trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl are more preferred.

[0092] In this specification, the "cycloalkyl (group)" refers to a cyclic alkyl. When the number of carbon atoms is not particularly limited, it is preferably C 3-15 cycloalkyl, more preferably C 3-8 cycloalkyl.

[0093] In this specification, "C 3-15The term "cycloalkyl (group)" refers to a cyclic alkyl group having 3 to 15 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, and cyclopentadecyl. 3-8 The term "cycloalkyl (group)" refers to a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Among them, C 3-6 Cycloalkyl.

[0094] In the present specification, an "alkoxy (group)" refers to a group in which a linear or branched alkyl group is bonded to an oxygen atom.

[0095] In this manual, "C 1-30 The term "alkoxy (group)" refers to 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, pentoxy, isopentoxy, neopentoxy, hexoxy, isohexoxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, heptoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, and triacosyloxy.

[0096] In this manual, "C 1-6 The term "alkoxy (group)" refers to 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, and hexyloxy. Among them, C 1-4 Alkoxy.

[0097] In this specification, "halogenated C 1-30 Alkoxy (group)" refers to the aforementioned "C 1-30"alkoxy" group in which one or more hydrogen atoms are substituted by a halogen atom. Specifically, for example, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, heptafluoropropoxy, 2,2-difluoropropoxy, 1,1,2,2-tetrafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2-difluorobutoxy, 2,2,3,3,3-pentafluoropropoxy, 4,4,4-trifluorobutoxy, 2,2-difluoropentyloxy, 5,5,5-trifluoropentyloxy, 2,2-difluorohexyloxy, 6,6,6-trifluorohexyloxy, etc. are mentioned. Among them, the aforementioned "C 1-6 "Halo-C" in which one or more hydrogen atoms in an alkoxy group are replaced by a halogen atom 1-6 Alkoxy".

[0098] In this specification, "fluorinated C 1-6 Alkoxy (group)" refers to the aforementioned "halogenated C 1-6 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, heptafluoropropoxy, 2,2-difluoropropoxy, 1,1,2,2-tetrafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2-difluorobutoxy, 1,2,3,3,3-pentafluoropropoxy, 4,4,4-trifluorobutoxy, 2,2-difluoropentyloxy, 5,5,5-trifluoropentyloxy, 2,2-difluorohexyloxy, 6,6,6-trifluorohexyloxy, etc. Among them, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, etc. are preferred. 1-4 The alkoxy (group)" is more preferably a difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy or pentafluoroethoxy, particularly preferably a trifluoromethoxy.

[0099] In this specification, "aryl" refers to a monocyclic or polycyclic (condensed) hydrocarbon group showing aromaticity, and specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthrenyl, 9-phenanthrenyl, etc. 6-14 Among them, phenyl, 4-biphenyl, 1-naphthyl or 2-naphthyl is preferred.

[0100] In this specification, "substituted with one or more fluorine atoms or one or more fluorinated C 1-4 Alkyl substituted C 6-14 "Aryl" refers to the aforementioned C 6-14 One or more hydrogen atoms in the aryl group are replaced by fluorine atoms or fluorinated C 1-4 Specific examples of the alkyl-substituted group include pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl, 1,3,4,5,6,7,8-heptafluoro-2-naphthyl, 4-trifluoromethylphenyl, and 3,4-bis(trifluoromethyl)phenyl. Among them, pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl, and 1,3,4,5,6,7,8-heptafluoro-2-naphthyl are preferred.

[0101] In this manual, "C 6-14 Aryl substituted and C 6-14 The aryl group is substituted with one or more fluorine atoms. 1-30 "Alkyl (group)" refers to: 6-14 One or more hydrogen atoms in the aryl group are replaced by fluorine atoms to obtain a group-substituted C 1-30 Alkyl, preferably C substituted by phenyl or naphthyl 1-6 The alkyl group is substituted with one or more fluorine atoms for each of the phenyl and naphthyl groups. Specifically, examples include pentafluorophenylmethyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl)methyl, 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl, and 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl. Among them, pentafluorophenylmethyl, 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl, and 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl are preferred, and pentafluorophenylmethyl is more preferred.

[0102] In this manual, R 6 and R 7 The "cyclic group" formed by the mutually bonded groups and the nitrogen atom to which they are bonded refers to a cyclic ammonium group (ammonio group) derived from a saturated nitrogen-containing non-aromatic heterocyclic group (in the case of the compound of the present invention (compound (1))) or a saturated nitrogen-containing non-aromatic heterocyclic ring (in the case of the compound (3) described later). Here, the "cyclic ammonium group derived from a saturated nitrogen-containing non-aromatic heterocyclic group" refers to a group formed by R 6 and R 7A cyclic ammonium group formed by mutual key combination and bonding a hydrogen atom to the nitrogen atom to which they are bonded. As the "cyclic group", as other ring-forming atoms other than the nitrogen atom of the amino group, in addition to carbon atoms, heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms are optionally present, and cyclic ammonium groups derived from monocyclic nitrogen-containing non-aromatic heterocyclic groups of 3 to 8 members (preferably 4 to 6 members) can be cited. As a specific example of the "cyclic group", cyclic ammonium groups derived from aziridinyl, azetidinyl, pyrrolidinyl, pyrroline, piperidinyl, azepanyl, morpholinyl, thiomorpholinyl, piperazinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, oxazolinyl, thiazolinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl group, tetrahydropyridyl, tetrahydropyrimidinyl, tetrahydrotriazolinyl and other 3 to 8 membered monocyclic nitrogen-containing non-aromatic heterocyclic groups can be cited. Among them, cyclic ammonium groups derived from azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl are preferred, and cyclic ammonium groups derived from piperidinyl or piperazinyl are more preferred. The "saturated nitrogen-containing non-aromatic heterocycle" can be cited as a monocyclic nitrogen-containing non-aromatic heterocycle of 3 to 8 members (preferably 4 to 6 members). In this heterocycle, as other ring-forming atoms other than the nitrogen atom of the amino group, in addition to carbon atoms, heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms are optionally present. As a specific example of the "saturated nitrogen-containing non-aromatic heterocycle", aziridine, azetidine, pyrrolidine, pyrroline, piperidine, azepane, morpholine, thiomorpholine, piperazine, oxazolidine, thiazolidine, imidazolidine, oxazoline, thiazoline, imidazoline, pyrazolidine, pyrazoline, tetrahydropyridine, tetrahydropyrimidine, tetrahydrotriazoline and other 3 to 8 membered monocyclic nitrogen-containing non-aromatic heterocycles can be cited. Among them, azetidine, pyrrolidine, piperidine, piperazine or morpholine is preferred, and piperidine or piperazine is more preferred.

[0103] In this specification, "optionally substituted" means unsubstituted or having one or more substituents. As the "substituent", as long as not specifically mentioned, (1) a halogen atom, (2) a nitro group, (3) a cyano group, (4) C 1-30 alkyl, (5) halo C 1-30 alkyl, (6) C 3-8 cycloalkyl, (7) C 1-30 alkoxy, (8) halo C 1-30 alkoxy, (9) C 6-14 aryl, etc. Among them, a halogen atom, a cyano group, C 1-6 alkyl, halo C 1-6 alkyl, C 1-6 alkoxy, halo C 1-6 alkoxy or phenyl are preferred, and a halogen atom (for example, a fluorine atom), C 1-4 alkyl (for example, methyl, ethyl), C 1-4Alkoxy (e.g. methoxy, ethoxy), halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) or halogenated C 1-4 Alkoxy (e.g. trifluoromethoxy, 2,2,2-trifluoroethoxy, etc. fluorinated C 1-4 In addition, when there are multiple substituents, each substituent may be the same or different. In addition, the above substituents may be further replaced by one or more C 1-6 Alkyl, C 1-6 It may be substituted by an alkoxy group, a halogen atom, a phenyl group or the like.

[0104] In this specification, specific examples of the “alkali metal ion” include lithium ion, potassium ion, sodium ion, and cesium ion.

[0105] In this specification, specific examples of the “alkaline earth metal ion” include magnesium ion and calcium ion.

[0106] In this specification, the term "hydrocarbon solvent" refers to a solvent including an aromatic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent. Among them, aliphatic hydrocarbon solvents are preferred from the viewpoint of odor and toxicity.

[0107] In this specification, examples of the “aromatic hydrocarbon solvent” include benzene, toluene, and xylene.

[0108] In the present specification, examples of the "aliphatic hydrocarbon solvent" include n-hexane, isohexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and mixed solvents thereof.

[0109] In this specification, the term "soluble in a hydrocarbon solvent (or aliphatic hydrocarbon solvent)" means that, at 25°C, the compound (or composition) of the present invention dissolves at a concentration of 5% by weight or more in a solution of a hydrocarbon solvent (or aliphatic hydrocarbon solvent) and the compound (or composition) of the present invention to form a transparent, uniform solution. Furthermore, the term "readily soluble in a hydrocarbon solvent (or aliphatic hydrocarbon solvent)" means that, at 25°C, the compound (or composition) of the present invention dissolves at a concentration of 20% by weight or more (preferably 30% by weight or more) in a solution of a hydrocarbon solvent (or aliphatic hydrocarbon solvent) and the compound (or composition) of the present invention to form a transparent, uniform solution.

[0110] (Compound of the present invention)

[0111] Hereinafter, the compound of the present invention will be described.

[0112] The compound of the present invention is a compound represented by the following formula (1).

[0113]

[0114] [Where,

[0115] R 1 , R 2 , R 3 and R 4 Each independently represents a fluorine atom or a fluorinated C 1-4 Alkyl substituted C 6-14 Aryl,

[0116] R 5 represents C substituted with one or more substituents 1-30 Alkyl, the substituent is selected from C 6-14 A group consisting of an aromatic group and a fluorine atom,

[0117] R 6 and R 7 Each independently represents an optionally substituted C 1-30 Alkyl, optionally substituted C 3-15 Cycloalkyl or optionally substituted C 6-14 Aryl, or

[0118] R 6 and R 7 are bonded to each other and to the nitrogen atom to which they are bonded to form an optionally substituted cyclic group,

[0119] n represents 1, and

[0120] m represents 1 or 2.]

[0121] Preferred embodiments of the compound represented by formula (1) (hereinafter also referred to as "compound (1)") are described below.

[0122] Hereinafter, each group of compound (1) will be described.

[0123] R 1 , R 2 , R 3 and R 4 Preferably, each independently is substituted with one or more fluorine atoms or one or more fluorinated C 1-4 alkyl (e.g., trifluoromethyl)-substituted, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthrenyl or 9-phenanthrenyl, more preferably phenyl, 1-naphthyl, 2-naphthyl or 4-biphenylyl, each independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups, particularly preferably R 1 , R 2 , R 3 and R 4All are the same pentafluorophenyl, 2,2’,3,3’,4’,5,5’,6,6’-nonafluoro-4-(1,1’-biphenyl)yl, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl.

[0124] R 5 Preferably a C substituted by a phenyl or naphthyl 1-6 alkyl, or a fluorinated C 1-6 alkyl, wherein the phenyl or naphthyl is each substituted by one or more fluorine atoms, more preferably phenylmethyl substituted by one or more fluorine atoms (such as pentafluorophenylmethyl), or fluorinated C 1-6 alkyl, still more preferably fluorinated C 1-6 alkyl (such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc., fluorinated C 1-6 alkyl having fluorine atoms at the β-position and / or γ-position), particularly preferably fluorinated C 1-4 alkyl (such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc., fluorinated C 1-4 alkyl having a fluorine atom at the β-position).

[0125] R 6 and R 7 Preferably each independently is a C optionally substituted by a substituent selected from the group consisting of (1) an optionally halogen atom-substituted C 6-14 aryl, (2) a halogen atom, and (3) a C 1-30 alkoxy; or 1-30

[0126] optionally a C substituted by a substituent selected from the group consisting of (1) a halogen atom, (2) a C 1-30 alkyl, (3) a C 1-30 alkoxy, (4) a halogenated C 1-30 alkyl, and (5) a halogenated C 1-30 alkoxy; 3-8 6-14 cycloalkyl,

[0127] More preferably each independently is a C optionally substituted by a substituent selected from the group consisting of (1) an optionally halogen atom (such as a fluorine atom)-substituted C 6-14 aryl, (2) a halogen atom, and (3) a C 1-30 alkoxy; 1-30alkyl.

[0128] As R 6 and R 7 Another way, preferably R 6 and R 7 They are bonded to each other and together with the nitrogen atom to which they are bonded form an optionally substituted cyclic group derived from a 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group, and more preferably R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 Alkyl (e.g., methyl, ethyl), (3)C 1-4 Alkoxy (e.g., methoxy, ethoxy), (4) halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) and (5) halogenated C 1-4 The cyclic group substituted by the substituent in the group consisting of alkoxy, derived from azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl, particularly preferably R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally substituted by a halogen atom (e.g., a fluorine atom), a C 1-4 Alkyl (such as methyl, ethyl), C 1-4 Alkoxy (e.g. methoxy, ethoxy), halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) or halogenated C 1-4 Alkoxy-substituted cyclic groups derived from piperidinyl or piperazinyl.

[0129] R 5 , R 6 and R 7 The total number of carbon atoms is preferably 25 or more, more preferably 35 or more.

[0130] n is preferably 1.

[0131] m is preferably 1 or 2, more preferably 1.

[0132] Examples of suitable compounds (1) include the following compounds.

[0133] [Compound (1-1)]

[0134] This is a compound (1) wherein the following groups in the aforementioned formula (1) are defined as follows:

[0135] R 1 , R 2 , R 3 and R4 Each independently is phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl or 9-phenanthryl, each substituted by one or more fluorine atoms or one or more fluorinated C 1-4 alkyl groups (such as trifluoromethyl),

[0136] R 5 is C 1-6 alkyl substituted by phenyl or naphthyl, or fluorinated C 1-6 alkyl (preferably 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc., fluorinated C 2-4 alkyl having a fluorine atom at the β-position and having three or more fluorine atoms), wherein the phenyl or naphthyl is each substituted by one or more fluorine atoms,

[0137] R 6 and R 7 each independently is C 6-14 alkyl optionally substituted by a substituent selected from the group consisting of (1) C 1-30 aryl optionally substituted by a halogen atom, (2) a halogen atom, and (3) C 1-30 alkoxy; or

[0138] is C 1-30 cycloalkyl optionally substituted by a substituent selected from the group consisting of (1) a halogen atom, (2) C 1-30 alkyl, (3) C 1-30 alkoxy, (4) halogenated C 1-30 alkyl, and (5) halogenated C 3-8 alkoxy, n is 1, and

[0139] m is 1.

[0140] [Compound (1-2)]

[0141] It is Compound (1) in which the following groups in the aforementioned formula (1) are defined as follows:

[0142] R 1 、R 2 、R 3 and R 4 each independently is phenyl, 1-naphthyl, 2-naphthyl or 4-biphenyl substituted by one or more fluorine atoms or one or more trifluoromethyl groups,

[0143] R 5 is phenylmethyl substituted by one or more fluorine atoms (such as pentafluorophenylmethyl) or fluorinated C 1-6 alkyl, more preferably fluorinated C 1-6Alkyl groups (such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc., which are fluorinated C alkyl groups having fluorine atoms at the β-position and / or γ-position), 1-6 preferably 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc., which are fluorinated C alkyl groups having fluorine atoms at the β-position and having 3 or more fluorine atoms, 2-4 alkyl groups,

[0144] R 6 and R 7 are each independently C alkyl groups optionally substituted with substituents selected from the group consisting of (1) C aryl groups optionally substituted with a halogen atom (such as a fluorine atom), (2) halogen atoms, and (3) C alkoxy groups, 6-14 aryl groups, (2) halogen atoms, and (3) C 1-30 alkyl groups, 1-30 alkyl groups,

[0145] n is 1, and

[0146] m is 1.

[0147] [Compound (1-3)]

[0148] Compound (1) in which the following groups in the aforementioned formula (1) are defined as follows:

[0149] R 1 、R 2 、R 3 and R 4 are all the same pentafluorophenyl, 2,2’,3,3’,4’,5,5’,6,6’-nonafluoro-4-(1,1’-biphenyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group,

[0150] R 5 is a fluorinated C 1-6 alkyl group (such as 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc., which are fluorinated C alkyl groups having fluorine atoms at the β-position and / or γ-position), 1-6 alkyl group),

[0151] R 6 and R 7 are each independently C alkyl groups optionally substituted with substituents selected from the group consisting of (1) C aryl groups optionally substituted with a halogen atom (such as a fluorine atom),6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 alkyl,

[0152] n is 1, and

[0153] m is 1.

[0154] [Compound (1-4)]

[0155] This is a compound (1) wherein the following groups in the aforementioned formula (1) are defined as follows:

[0156] R 1 , R 2 , R 3 and R 4 are all the same pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl,

[0157] R 5 Fluorinated C 1-4 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) 1-4 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl),

[0158] R 6 and R 7 are each independently C optionally substituted by (1) a halogen atom (eg, a fluorine atom) 6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 alkyl,

[0159] n is 1, and

[0160] m is 1.

[0161] [Compound (1-5)]

[0162] This is a compound (1) wherein the following groups in the aforementioned formula (1) are defined as follows:

[0163] R 1 , R 2, R 3 and R 4 Each independently is phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl or 9-phenanthryl substituted with one or more fluorine atoms or one or more fluorinated C 1-4 alkyl groups (such as trifluoromethyl),

[0164] R 5 is C 1-6 alkyl substituted with phenyl or naphthyl, or fluorinated C 1-6 alkyl (preferably 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc., fluorinated C 2-4 alkyl having fluorine atoms at the β-position and having three or more fluorine atoms), and the phenyl or naphthyl is each substituted with one or more fluorine atoms,

[0165] R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded form an optionally substituted cyclic group derived from a 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group,

[0166] n is 1, and

[0167] m is 1 or 2.

[0168] [Compound (1-6)]

[0169] It is Compound (1) in which the following groups in the aforementioned formula (1) are defined as follows:

[0170] R 1 , R 2 , R 3 and R 4 Each independently is phenyl, 1-naphthyl, 2-naphthyl or 4-biphenyl substituted with one or more fluorine atoms or one or more trifluoromethyl groups,

[0171] R 5 is phenylmethyl substituted with one or more fluorine atoms (such as pentafluorophenylmethyl) or fluorinated C 1-6 alkyl, more preferably fluorinated C 1-6 alkyl (examples include 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc., fluorinated C 1-6Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl),

[0172] R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 Alkyl (e.g., methyl, ethyl), (3)C 1-4 Alkoxy (e.g., methoxy, ethoxy), (4) halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) and (5) halogenated C 1-4 a cyclic group derived from azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl, substituted by a substituent in the group consisting of alkoxy,

[0173] n is 1, and

[0174] m is 1 or 2.

[0175] [Compound (1-7)]

[0176] This is a compound (1) wherein the following groups in the aforementioned formula (1) are defined as follows:

[0177] R 1 , R 2 , R 3 and R 4 are all the same, pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl)yl, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl,

[0178] R 5 Fluorinated C 1-6 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.) having a fluorine atom at the β-position and / or γ-position; 1-6 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl),

[0179] R6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 Alkyl (e.g., methyl, ethyl), (3)C 1-4 Alkoxy (e.g., methoxy, ethoxy), (4) halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) and (5) halogenated C 1-4 A cyclic group derived from piperidinyl or piperazinyl substituted with a substituent in the group consisting of an alkoxy group,

[0180] n is 1, and

[0181] m is 1 or 2.

[0182] [Compound (1-8)]

[0183] This is a compound (1) wherein the following groups in the aforementioned formula (1) are defined as follows:

[0184] R 1 , R 2 , R 3 and R 4 are all the same, pentafluorophenyl, 2,2',3,3',4',5,5',6,6'-nonafluoro-4-(1,1'-biphenyl)yl, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl,

[0185] R 5 Fluorinated C 1-4 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) 1-4 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl),

[0186] R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 Alkyl (e.g., methyl, ethyl), (3)C 1-4 Alkoxy (e.g., methoxy, ethoxy), (4) halogenated C 1-4An alkyl group (such as a fluorinated C alkyl group like trifluoromethyl, 2,2,2-trifluoroethyl, etc.) and (5) a cyclic group derived from a piperidinyl group substituted with a substituent selected from the group consisting of a halogenated C alkoxy group, 1-4 alkyl group) and (5) a halogenated C 1-4 alkoxy group,

[0187] n is 1, and

[0188] m is 1.

[0189] As a preferred specific example of the compound (1), compounds such as those in Examples 1, 4 to 21, 23, and 25 described below can be cited.

[0190] (The composition of the present invention)

[0191] Hereinafter, the composition of the present invention will be described.

[0192] The composition of the present invention is a composition containing the aforementioned compound (1) (the compound of the present invention) and a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)").

[0193]

[0194] [In the formula,

[0195] R and R' each independently represent an optionally substituted C 1-30 alkyl group, an optionally substituted C 3-15 cycloalkyl group, or an optionally substituted C 6-14 aryl group.]

[0196] The composition containing the compound (1) and the compound (2) is not particularly limited as long as it contains the two compounds, and may contain a compound in which the compound (2) is coordinated to the compound (1) to form a complex. The composition of the present invention is preferably a composition containing a complex formed by the compound (1) and the compound (2).

[0197] A preferred embodiment of the compound (2) will be described below.

[0198] Hereinafter, each group of the compound (2) will be described.

[0199] R and R' are each independently an optionally substituted C 1-30 alkyl group, an optionally substituted C 3-15 cycloalkyl group, or an optionally substituted C 6-14 aryl group; preferably each independently an optionally substituted C alkyl group selected from the group consisting of (1) a halogen atom, (2) a C 1-30 alkoxy group, and (3) a halogenated C 1-30 alkoxy group, and an optionally substituted C 1-30 alkyl group selected from the group consisting of (1) a halogen atom, (2) a C1-30 Alkyl, (3)C 1-30 Alkoxy, (4)halo-C 1-30 Alkyl and (5)halo-C 1-30 C substituted with a substituent selected from the group consisting of alkoxy 3-15 Cycloalkyl, or optionally selected from (1) a halogen atom, (2)C 1-30 Alkyl, (3)C 1-30 Alkoxy, (4)halo-C 1-30 Alkyl and (5)halo-C 1-30 C substituted with a substituent selected from the group consisting of alkoxy 6-14 Aryl,

[0200] More preferably, each is independently C 1-30 Alkyl; C 3-8 Cycloalkyl (such as cyclopentyl, cyclohexyl, etc.); or optionally selected from (1) a halogen atom, (2)C 1-6 Alkyl, (3)C 1-6 Alkoxy, (4)halo-C 1-6 Alkyl and (5)halo-C 1-6 Phenyl substituted with a substituent selected from the group consisting of alkoxy

[0201] Even more preferably, each is independently C 1-30 Alkyl (preferably methyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc. C 1-18 Alkyl).

[0202] As a preferred specific example of the compound (2), dibutyl ether, dihexyl ether, dioctyl ether, didecyl ether, didodecyl ether, ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, cyclopentylmethyl ether, diphenyl ether, phenyl octadecyl ether, etc. can be mentioned, for example.

[0203] In the composition of the present invention, the content of the compound (2) is preferably in the range of 0.01 to 10 moles, more preferably in the range of 0.1 to 3 moles, relative to 1 mole of the compound (1).

[0204] As a preferred specific example of the composition of the present invention, the compositions of Examples 2, 3, 24, 26 to 34 described later can be mentioned, for example.

[0205] As another aspect of the composition of the present invention, a composition containing the aforementioned compound (1) (the compound of the present invention) and a compound represented by the following formula (3) (hereinafter also referred to as "compound (3)") (wherein, in this composition, the compound (3) is an amine compound obtained by deprotonating the cation constituting the aforementioned compound (1)).).

[0206]

[0207] [R in the formula 5 , R 6 and R 7 Means the same as above.]

[0208] A preferred embodiment of compound (3) is that except for R 6 and R 7 In addition to being deprotonated when bonded to each other and forming a cyclic group together with the nitrogen atom to which they are bonded, the groups (R 5 , R 6 and R 7 ) are preferred in the same manner.

[0209] Examples of suitable compounds (3) include the following compounds.

[0210] [Compound (3-1)]

[0211] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0212] R 5 C substituted by phenyl or naphthyl 1-6 Alkyl, or fluorinated C 1-6 Alkyl (preferably a fluorinated C group having 3 or more fluorine atoms at the β position, such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl) 2-4 alkyl), the phenyl or naphthyl group is substituted by one or more fluorine atoms, and

[0213] R 6 and R 7 Each is independently selected from (1) C optionally substituted by a halogen atom 6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 Alkyl; or

[0214] Optionally selected from (1) halogen atoms, (2) C 1-30 Alkyl, (3)C 1-30 Alkoxy, (4) halogenated C 1-30 Alkyl and (5) halogenated C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 3-8 Cycloalkyl.

[0215] [Compound (3-2)]

[0216] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0217] R5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., pentafluorophenylmethyl) or a fluoro-C 1-6 Alkyl, more preferably fluorinated C 1-6 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.) having a fluorine atom at the β-position and / or γ-position; 1-6 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl), and

[0218] R 6 and R 7 Each is independently optionally selected from (1) C optionally substituted by a halogen atom (such as a fluorine atom) 6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 alkyl.

[0219] [Compound (3-3)]

[0220] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0221] R 5 Fluorinated C 1-6 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.) having a fluorine atom at the β-position and / or γ-position; 1-6 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl), and

[0222] R 6 and R 7 Each is independently optionally selected from (1) C optionally substituted by a halogen atom (such as a fluorine atom) 6-14 Aryl group, (2) halogen atom and (3) C 1-30 The substituents in the group consisting of alkoxy groups are substituted with C 1-30 alkyl.

[0223] [Compound (3-4)]

[0224] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0225] R 5 Fluorinated C 1-4 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.) 1-4 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl), and

[0226] R 6 and R 7 Each is independently C optionally substituted by a substituent 1-30 Alkyl, the substituent being selected from C 6-14 Aryl groups, halogen atoms and C 1-30 A group consisting of alkoxy groups.

[0227] [Compound (3-5)]

[0228] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0229] R 5 C substituted by phenyl or naphthyl 1-6 Alkyl, or fluorinated C 1-6 Alkyl (preferably a fluorinated C group having 3 or more fluorine atoms at the β position, such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl) 2-4 alkyl), the phenyl or naphthyl group is substituted by one or more fluorine atoms, and

[0230] R 6 and R 7 They are bonded to each other and together with the nitrogen atom to which they are bonded, form an optionally substituted 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocycle.

[0231] [Compound (3-6)]

[0232] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0233] R 5 is a phenylmethyl group substituted with one or more fluorine atoms (e.g., pentafluorophenylmethyl) or a fluoro-C1-6 Alkyl, more preferably fluorinated C 1-6 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.) having a fluorine atom at the β-position and / or γ-position; 1-6 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl), and

[0234] R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C 1-4 Alkyl (e.g., methyl, ethyl), (3)C 1-4 Alkoxy (e.g., methoxy, ethoxy), (4) halogenated C 1-4 Alkyl (e.g. trifluoromethyl, 2,2,2-trifluoroethyl, etc. fluorinated C 1-4 Alkyl) and (5) halogenated C 1-4 The substituents in the group consisting of alkoxy are substituted, azetidine, pyrrolidine, piperidine, piperazine or morpholine.

[0235] [Compound (3-7)]

[0236] This is a compound (3) wherein the following groups in the aforementioned formula (3) are defined as follows:

[0237] R 5 Fluorinated C 1-6 Alkyl (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.) having a fluorine atom at the β-position and / or γ-position; 1-6 Alkyl groups, among which 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, and fluorinated C groups having 3 or more fluorine atoms at the β position are preferred. 2-4 alkyl), and

[0238] R 6 and R 7 bonded to each other and to the nitrogen atoms to which they are bonded, respectively, to form a group optionally selected from (1) a halogen atom (e.g., a fluorine atom), (2) C1-4 Alkyl (such as methyl, ethyl), (3)C 1-4 Alkoxy (such as methoxy, ethoxy), (4)halo C 1-4 Alkyl (such as trifluoromethyl, 2,2,2-trifluoroethyl and other fluoro C 1-4 alkyl) and (5)halo C 1-4 Alkoxy-substituted piperidine or piperazine selected from the group consisting of substituents.

[0239] [Compound (3-8)]

[0240] It is a compound (3) in which the following group in the aforementioned formula (3) is defined as follows:

[0241] R 5 Is fluoro C 1-4 Alkyl (examples include 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl and other fluoro C 1-4 Alkyl having a fluorine atom at the β-position, preferably 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and other fluoro C 2-4 Alkyl having a fluorine atom at the β-position and having 3 or more fluorine atoms), and

[0242] R 6 And R 7 Are bonded to each other and together with the nitrogen atom to which they are bonded, respectively form a piperidine optionally substituted with substituents selected from the group consisting of (1) halogen atoms (such as fluorine atoms), (2)C 1-4 Alkyl (such as methyl, ethyl), (3)C 1-4 Alkoxy (such as methoxy, ethoxy), (4)halo C 1-4 Alkyl (such as trifluoromethyl, 2,2,2-trifluoroethyl and other fluoro C 1-4 Alkyl) and (5)halo C 1-4 Alkoxy-substituted piperidine.

[0243] As preferred specific examples of the compound (3), for example, fluoroalkylamines, fluoroalkyl cyclic amines, etc. used in the synthesis of the compounds in Examples 1 and 4 to 21 described below can be cited.

[0244] In the composition of the present invention containing the compound (1) and the compound (3), relative to 1 mole of the compound (1), the content of the compound (3) is preferably in the range of 0.01 to 10 moles, more preferably in the range of 0.5 to 3 moles.

[0245] As a preferred specific example of the composition of the present invention containing compound (1) and compound (3), for example, the composition of Example 22 described later can be cited.

[0246] In the composition of the present invention containing compound (1) and compound (3), on the basis of containing compound (1) and compound (3), the aforementioned compound (2) may further be contained.

[0247] The preferred mode of compound (2) that may further be contained is the same as the preferred mode of each group (R and R') in the aforementioned compound (2) and its preferred specific examples. In addition, in the composition of the present invention containing compound (1), compound (2) and compound (3), with respect to 1 mole of compound (1), the contents of compound (2) and compound (3) are the same as those described above.

[0248] Among the compounds or compositions of the present invention, when the total number of carbon atoms of R 5 、R 6 and R 7 in the aforementioned formula (1) is 25 or more, it is soluble in aliphatic hydrocarbon solvents at room temperature (15 to 30 °C). In contrast, known borate compounds (such as tetrakis(pentafluorophenyl)borate hydride, tetrakis(pentafluorophenyl)borate hydride - diethyl ether complex, lithium tetrakis(pentafluorophenyl)borate, etc.) are insoluble in aliphatic hydrocarbon solvents such as n-hexane. Therefore, generally known borate compounds are used in the form of a solution in aromatic hydrocarbon solvents for polymerization reactions. As a result, it is necessary to remove the mixed aromatic hydrocarbon solvents, and with the increase in the number of processes, there are problems such as high commercial costs. In addition, sometimes it is also used in the form of a suspension in aliphatic hydrocarbon solvents, but there are problems such as poor operability due to suspension and the need for an excess. Therefore, the compounds or compositions of the present invention that are soluble in aliphatic hydrocarbon solvents are particularly useful as cocatalysts for the polymerization reactions of olefins, dienes, and acetylenes in a homogeneous system using hydrocarbon solvents (wherein aliphatic hydrocarbon solvents).

[0249] (Method for manufacturing the compound of the present invention)

[0250] Hereinafter, the method for manufacturing the compound (or composition) of the present invention (hereinafter also referred to as "the manufacturing method of the present invention") will be described.

[0251] The method for manufacturing the compound (or composition) of the present invention is not particularly limited, and it can be manufactured, for example, according to the following Production Methods 1 to 3 or the methods described in the following production examples or examples. In particular, by using the following production methods to manufacture fluoroalkylamines, the compounds (or compositions) of the present invention can be obtained with simpler operations, lower costs, and higher yields compared to conventional methods. Therefore, it can be an industrial production method.

[0252] (Production Method 1)

[0253] Preparation method 1 comprises: a step of reacting a dialkylamine compound (5) with a fluoroalkylcarboxylic anhydride (6) in the presence of a base in a solvent that does not affect the reaction to obtain a compound (7) (step 1); a step of reducing the compound (7) with a reducing agent in a solvent that does not affect the reaction to convert it into a compound (3a) (step 2); and a step of reacting the compound (3a) with a compound (4) in the presence of an acid in a solvent that does not affect the reaction to obtain a compound (1a) (a compound of the present invention) (step 3).

[0254]

[0255] (Where R 8 represents C substituted with one or more substituents 1-29 Alkyl, the substituent is selected from C 6-14 The group consisting of an aryl group and a fluorine atom, and the definitions of other symbols are the same as those above.)

[0256] (Process 1)

[0257] Examples of the solvent used in this step include hydrocarbon solvents such as toluene, n-hexane, isohexane, n-heptane, n-octane, cyclohexane, and methylcyclohexane; ethers such as diethyl ether and tetrahydrofuran; halogenated solvents such as chloroform and dichloromethane; and mixed solvents thereof, preferably a mixed solvent of toluene and tetrahydrofuran.

[0258] The amount of compound (6) used is usually 1 to 3 mol, preferably 1 to 2 mol, more preferably 1.2 mol, based on 1 mol of compound (5).

[0259] Examples of the base used in this step include organic bases such as triethylamine, N,N-diisopropylethylamine, pyridine, and 2,6-lutidine. Among them, triethylamine is preferred.

[0260] The amount of the base used is usually 1 to 3 mol, preferably 1 to 2 mol, more preferably 1.2 mol, based on 1 mol of compound (5).

[0261] The reaction temperature is usually 0 to 40°C, preferably 10 to 35°C, more preferably room temperature (15 to 30°C). The reaction time is usually about 10 minutes to 10 hours, preferably about 30 minutes to 2 hours.

[0262] In Preparation Method 1, the compound (7) prepared as described above can be used in Step 2 as it is.

[0263] (Process 2)

[0264] The solvent used in this step is not particularly limited, and examples thereof include ethers such as triethylene glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, and dioxane. Among them, tetrahydrofuran is preferred.

[0265] Examples of the reducing agent used in this step include boron hydrides or aluminum hydrides. Specific examples of the reducing agent are not particularly limited, and examples thereof include sodium borohydride, lithium borohydride, lithium aluminum hydride, borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, sodium borohydride / trifluoroacetic acid, etc. Among them, borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, sodium borohydride / trifluoroacetic acid and other boron hydrides are preferred.

[0266] The amount of the reducing agent such as borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, sodium borohydride / trifluoroacetic acid is usually 2 to 10 moles, preferably 2 to 3 moles, relative to 1 mole of the compound (7).

[0267] The reaction temperature is the reflux temperature of the commonly used solvent, preferably 40 °C to 80 °C.

[0268] The reaction time is usually about 30 minutes to 10 hours, preferably about 1 to 4 hours.

[0269] (Step 3)

[0270] The solvent used in this step is not particularly limited, and examples thereof include halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, and trichloroethylene; hydrocarbon solvents such as toluene, n-hexane, iso-hexane, n-heptane, n-octane, cyclohexane, and methylcyclohexane. Among them, dichloromethane, chloroform, n-hexane, iso-hexane, n-heptane, cyclohexane, methylcyclohexane, etc. are preferred, and dichloroethane, chloroform, n-hexane, iso-hexane, n-heptane or methylcyclohexane are particularly preferred.

[0271] Examples of the acid used in this step include proton acids such as hydrogen bromide, hydrogen chloride, and hydrogen iodide. Among them, hydrogen chloride is preferred. As hydrogen chloride, commercially available products (1.0 M hydrogen chloride-diethyl ether solution or hydrochloric acid) can be directly used.

[0272] The amount of the acid is usually 1 to 5 moles, preferably 1 to 2 moles, relative to 1 mole of the compound (3a).

[0273] As the compound (4) used in this step, there is no particular limitation. Commercially available products or purified products can be used. In addition, compounds prepared by publicly known methods can also be used. Specific examples of the compound (4) include, for example, lithium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, lithium tetrakis(heptafluoronaphthyl)borate, potassium tetrakis(heptafluoronaphthyl)borate, chloromagnesium tetrakis(pentafluorophenyl)borate, chloromagnesium tetrakis(heptafluoronaphthyl)borate, bromomagnesium tetrakis(pentafluorophenyl)borate, bromomagnesium tetrakis(heptafluoronaphthyl)borate, lithium tetrakis(nonafluorobiphenyl)borate, potassium tetrakis(nonafluorobiphenyl)borate, chloromagnesium tetrakis(nonafluorobiphenyl)borate, bromomagnesium tetrakis(nonafluorobiphenyl)borate, tris(diethyl ether) complex of lithium tetrakis(pentafluorophenyl)borate, mono(diethyl ether) complex of lithium tetrakis(pentafluorophenyl)borate, and the like.

[0274] The amount of the compound (4) is usually 1 to 1.5 moles, preferably 1 mole, relative to 1 mole of the compound (3a).

[0275] The reaction temperature is usually 0°C to 80°C, preferably 15°C to 60°C, and the reaction time is usually about 10 minutes to 10 hours, preferably about 1 to 3 hours.

[0276] (Production Method 2)

[0277] Production Method 2 is a method for obtaining a composition (the composition of the present invention) containing the compound (1a) and the compound (2) by carrying out the reaction of Step 3 of the aforementioned Production Method 1 in the presence of the compound (compound (2)) represented by the formula (2). Except for adding the compound (2), it can be carried out in the same manner as Step 3 of the aforementioned Production Method 1.

[0278]

[0279] [The definitions of the symbols in the formula are the same as the aforementioned meanings.]

[0280] The amount of the compound (2) is usually 0.01 to 10 moles, preferably 0.1 to 3 moles, relative to 1 mole of the compound (4).

[0281] (Production Method 3)

[0282] Production Method 3 is a method for obtaining a composition (the composition of the present invention) containing the compound (1a) and the compound (3a) by using an excessive amount of the compound (3a) in the reaction of Step 3 of the aforementioned Production Method 1. Except for using an excessive amount of the compound (3a), it can be carried out in the same manner as Step 3 of the aforementioned Production Method 1.

[0283] The amount of the compound (3a) is usually 1.01 to 11 moles, preferably 1.1 to 4 moles, relative to 1 mole of the compound (4).

[0284] The compound (Compound (1)) of the present invention or the composition of the present invention is a compound or composition derived from a fluoroalkylamine, and thus substantially does not contain compounds such as amine compounds with high basicity and nucleophilicity that can form catalyst poisons. Therefore, it is useful as a cocatalyst for the polymerization of olefins, dienes, and acetylenes.

[0285] The present invention includes a method for manufacturing a polymer, which includes: using the compound (Compound (1)) of the present invention or the composition of the present invention as a cocatalyst to polymerize at least one monomer selected from the group consisting of olefins, dienes, and acetylenes.

[0286] Specifically, the manufacture of a polymer using the compound (Compound (1)) (or composition) of the present invention as a cocatalyst can be carried out according to the method described in the test examples below, for example.

[0287] Examples

[0288] Hereinafter, the present invention will be specifically described by way of examples, production examples, and test examples, but the present invention is not limited to these examples and the like. Regarding the yield, % represents mol / mol%, and for others, unless otherwise specified, % represents weight %. In addition, unless otherwise specified, room temperature represents a temperature of 15°C to 30°C.

[0289] Unless otherwise specified, the solvents and reagents used in the following examples were purchased from suppliers such as Sigma Aldrich, Tokyo Chemical Industry Co., Ltd., Fujifilm Wako Pure Chemical Corporation, Junsei Chemical Co., Ltd., Kanto Chemical Co., Inc., and Combi-Blocks. In addition, the deuterated solvents used in NMR measurements were purchased from Cambridge Isotope Laboratories.

[0290] It should be noted that the following machines were used for analysis.

[0291] 1 H-NMR and 19 F-NMR: 400YH manufactured by JEOL Ltd.

[0292] [Production Example 1]

[0293] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroacetamide

[0294] N,N-dioctadecylamine (2.0 g, 3.8 mmol) and triethylamine (0.5 g, 5.0 mmol) were dissolved in tetrahydrofuran (10 mL), and trifluoroacetic anhydride (1.0 g, 4.8 mmol) was added at room temperature. Stir at room temperature for 1 hour, add water, and extract with ethyl acetate. The organic layer was washed with 1 M hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (1.87 g, 79%).

[0295] 1 H NMR(CDCl3)δ:0.89(6H,t),1.26-1.43(60H,m),1.56-1.59(4H,m),3.30-3.37(4H,m);

[0296] 19 F NMR (CDCl3) δ: -70.1 (3F, s).

[0297] [Production Example 2]

[0298] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylamine

[0299] N,N-dioctadecyl-2,2,2-trifluoroacetamide (1.0 g, 1.6 mmol) obtained in Preparation Example 1 was dissolved in tetrahydrofuran (10 mL), and a 1 M solution of borane-tetrahydrofuran complex in tetrahydrofuran (5 mL) was added, followed by reflux for 3 hours. After the mixture was ice-cooled, water was carefully added dropwise, and extraction was performed with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the title compound (0.87 g, 88%).

[0300] 1 H NMR(CDCl3)δ:0.88(6H,t),1.25-1.40(60H,m),1.42-1.44(4H,m),2.56(4H,t),3.00(2H,q);

[0301] 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0302] [Production Example 3]

[0303] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylamine hydrochloride

[0304] N,N-Dioctadecyl-2,2,2-trifluoroethylamine (1.0 g, 1.7 mmol) obtained in Preparation Example 2 was dissolved in n-hexane (10 mL), and a 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added. The mixture was stirred at room temperature for 3 hours. The resulting precipitate was collected by filtration, washed with n-hexane, and dried under reduced pressure to obtain the title compound (0.987 g, 93%).

[0305] 1 H NMR(CDCl3)δ:0.88(6H,t),1.19-1.40(60H,m),1.93(4H,br s),3.15(4H,brs),3.77(2H,q);

[0306] 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0307] [Example 1]

[0308] Synthesis of N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0309] N,N-Dioctadecyl-2,2,2-trifluoroethylamine hydrochloride (0.32 g, 0.5 mmol) obtained in Preparation Example 3 was dissolved in chloroform (30 mL). Lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.45 g, 0.5 mmol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.62 g, 97%).

[0310] 1 H NMR(CDCl3)δ:0.88(6H,t),1.19-1.40(60H,m),1.94(4H,br s),3.15(4H,brs),3.77(2H,q);

[0311] 19 F NMR(CDCl3)δ:-66.7(3F,t),-134.1(8H,m),-163.2(4H,m),-1675.5(8H,m).

[0312] [Example 2]

[0313] Synthesis of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and ditetradecyl ether

[0314] The N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (0.30 g, 0.22 mmol) obtained in Example 1 was mixed with ditetradecyl ether (0.09 g, 0.22 mmol) to obtain the title composition.

[0315] 1 H NMR(CDCl3)δ:0.85-0.90(12H,m),1.20-1.33(104H,m),1.52-1.68(8H,m),3.14-3.18(4H,m),3.40(4H,t),3.62(2H,q);

[0316] 19 F NMR(CDCl3)δ:-66.8(3F,br s),-134.0(8F,m),-163.2(4F,t),-167.5(8F,m).

[0317] N-hexane was added to the composition obtained in Example 2 to prepare a 20 wt % n-hexane solution, and the resulting solution was confirmed to be a uniform solution.

[0318] Isohexane was added to the composition obtained in Example 2 to prepare a 20 wt % isohexane solution, which was then confirmed to be a uniform solution.

[0319] n-heptane was added to the composition obtained in Example 2 to prepare a 20 wt % n-heptane solution, which was confirmed to be a uniform solution.

[0320] ISOPAR E (registered trademark) was added to the composition obtained in Example 2 to prepare a 20 wt % ISOPARE (registered trademark) solution, which was then confirmed to be a uniform solution.

[0321] Cyclohexane was added to the composition obtained in Example 2 to prepare a 20 wt% cyclohexane solution, which was then confirmed to be a uniform solution.

[0322] Methylcyclohexane was added to the composition obtained in Example 2 to prepare a 20 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0323] [Example 3]

[0324] Synthesis of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dibutyl ether

[0325] The N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (300 mg, 0.23 mmol) obtained in Example 1 was mixed with dibutyl ether (62 mg, 0.46 mmol) to obtain the title composition.

[0326] 1 H NMR(CDCl3)δ:0.87(6H,t),0.92(12H,t),1.20-1.68(78H,m),3.14-3.18(4H,m),3.41(8H,t),3.62(2H,q);

[0327] 19 F NMR(CDCl3)δ:-66.7(3F,s),-134.0(8F,s),-163.3(4F,t),-167.5(8H,m).

[0328] It was confirmed that the composition obtained in Example 3 was dissolved in n-hexane at 30% by weight.

[0329] [Example 4]

[0330] Synthesis of N,N-dioctadecyl-N-(2,2,2-trifluoroethyl)tetrakis(2-heptafluoronaphthyl)ammonium borate

[0331] A diethyl ether solution of lithium tetrakis(2-heptafluoronaphthyl)borate (46.9% by weight) (1.0 g, 0.46 mmol) prepared by a known method (see, for example, International Publication No. 2007 / 070770) and dioctadecyl-N-(2,2,2-trifluoroethyl)ammonium hydrochloride (0.292 g, 0.46 mmol) were added to 10 mL of dichloromethane. After stirring at room temperature, water was added to separate the layers. The organic layer was dried by adding anhydrous sodium sulfate and then concentrated to obtain the title compound (0.78 g) as a yellow solid.

[0332] 1 H NMR(CDCl3)δ:0.87(6H,t),1.24(60H,m),1.62(4H,m),3.20(4H,t),3.69(2H,q);

[0333] 19 F NMR(CDCl3)δ:-63.3(3F,t),-106.7(4F,m),-123.4(4F,m),-143.3(4F,m),-146.8(4F,m),-152.5(4F,m),-155.8(4F,m),-157.3(4F,m).

[0334] [Production Example 4]

[0335] Synthesis of N-Benzyl-N-methyl-2,2,2-trifluoroethylamine

[0336] N-methylbenzylamine (manufactured by Kanto Chemical Co., Ltd.) (1.1 g, 9.1 mmol) and triethylamine (1.5 g, 15 mmol) were mixed, and 2,2,2-trifluoroethyl trifluoromethanesulfonate (2.2 g, 9.5 mmol) was added at room temperature. The mixture was stirred overnight, 1 M hydrochloric acid was added, and extraction was performed with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (n-hexane / ethyl acetate = 98 / 2-90 / 10) to obtain the title compound (1.65 g, 86%).

[0337] 1 H NMR(CDCl3)δ:2.43(3H,s),3.03(2H,q),3.71(2H,s),7.25-7.34(5H,m); 19 FNMR (CDCl3) δ: -69.9 (3F, t).

[0338] [Production Example 5]

[0339] Synthesis of N-Benzyl-N-methyl-2,2,2-trifluoroethylamine Hydrochloride

[0340] A 1 M hydrogen chloride-diethyl ether solution (20 mL) was added to N-benzyl-N-methyl-2,2,2-trifluoroethylamine (1.65 g, 8.1 mmol) obtained in Preparation Example 4. The mixture was stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure to obtain the title compound (1.97 g, 100%).

[0341] 1 H NMR(CDCl3)δ:2.96(3H,s),3.70-3.81(2H,m),4.46(2H,s),7.41-7.52(3H,m),7.59-7.67(2H,m);

[0342] 19 F NMR(CDCl3)δ:-63.2(3F,br s).

[0343] [Example 5]

[0344] Synthesis of N-Benzyl-N-methyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0345] N-Benzyl-N-methyl-2,2,2-trifluoroethylamine hydrochloride (0.30 g, 1.25 mmol) obtained in Preparation Example 5 was dissolved in chloroform (30 mL). Lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (1.10 g, 1.21 mol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.07 g, 93%).

[0346] 1 H NMR(CDCl3)δ:2.97(3H,s),3.60(2H,q),4.33(2H,s),7.41-7.57(5H,m);

[0347] 19 F NMR(CDCl3)δ:-65.3(3F,t),-134.0(8H,m),-163.4(4F,t),-167.6(8F,m).

[0348] [Production Example 6]

[0349] Synthesis of N,N-bis(pentafluorophenylmethyl)-1-butylamine

[0350] Pentafluorobenzaldehyde (3.0 g, 15.3 mmol), 1-butylamine (0.50 g, 7.0 mmol) and acetic acid (0.40 g) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (3.50 g, 17.0 mmol) was added, and the mixture was stirred at room temperature for 15 hours. A saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-90 / 10) to obtain the title compound (2.65 g, 90%).

[0351] 1 H NMR(CDCl3)δ:0.81(3H,t),1.17-1.23(2H,m),1.43-1.48(2H,m),2.40(2H,t),3.71(4H,s).

[0352] 19 F NMR(CDCl3)δ:-143.8(4F,dd),-156.1(2H,t),-163.4(4F,m).

[0353] [Production Example 7]

[0354] Synthesis of N,N-bis(pentafluorophenylmethyl)-1-butylamine hydrochloride

[0355] Dissolve N,N-bis(pentafluorophenylmethyl)-1-butylamine (2.30 g, 5.1 mmol) obtained in Production Example 6 in n-hexane (30 mL), and add 1 M hydrogen chloride - diethyl ether (20 mL). Stir the mixture at room temperature for 1 hour, and distill off the solvent under reduced pressure to obtain the title compound (1.98 g, 80%).

[0356] 1 H NMR (CDCl3) δ: 0.99 (3H, t), 1.38 - 1.43 (2H, m), 2.03 - 2.11 (2H, m), 2.99 - 3.03 (2H, m), 4.36 (4H, m);

[0357] 19 F NMR (CDCl3) δ: -136.8 (4F, d), -147.9 (2F, t), -159.5 (4H, m).

[0358] [Example 6]

[0359] Synthesis of ammonium N,N-bis(pentafluorophenylmethyl)-1-butyltetrakis(pentafluorophenyl)borate

[0360] Dissolve N,N-bis(pentafluorophenylmethyl)-1-butylamine hydrochloride (0.93 g, 1.02 mmol) obtained in Production Example 7 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (0.50 g, 1.03 mol), stir at room temperature for 1 hour, and filter off the insoluble matter. Dissolve the insoluble matter in water and dichloromethane, and separate the organic layer. Dry the organic layer over anhydrous magnesium sulfate and concentrate under reduced pressure to obtain the title compound (0.65 g, 65%).

[0361] 1 H NMR (DMSO-d6) δ: 0.77 (3H, t), 1.13 - 1.22 (2H, m), 1.42 - 1.48 (2H, m), 2.43 - 2.50 (2H, m), 4.62 (2H, br s);

[0362] 19 F NMR (DMSO-d6) δ: -132.7 (8F, m), -143.0 (4F, br s), -156.3 (2F, br s), -161.7 (4F, t), -163.3 (4F, br s), -166.2 (8F, m).

[0363] [Production Example 8]

[0364] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine

[0365] Pentafluorobenzaldehyde (0.50 g, 2.60 mmol) and N,N-dioctadecylamine (1.50 g, 2.87 mmol) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (1.00 g, 4.72 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (1.05 g, 52%).

[0366] 1 H NMR(CDCl3)δ:0.88(6H,t),1.20-1.30(64H,m),2.38(4H,t),3.69(2H,s);

[0367] 19 F NMR(CDCl3)δ:-143.0(8F,m),-157.1(4F,m),-163.8(8F,m).

[0368] [Production Example 9]

[0369] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine hydrochloride: N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine (2.95 g, 4.2 mmol) obtained in Preparation Example 8 was dissolved in n-hexane (30 mL), and 1 M hydrogen chloride-diethyl ether (20 mL) was added. The reaction mixture was stirred at room temperature for 1 hour, and the solvent was evaporated under reduced pressure to obtain the title compound (3.05 g, 98%).

[0370] 1 H NMR(CDCl3)δ:0.88(6H,t),1.21-1.35(60H,m),1.88-1.93(4H,m),2.92-3.02(4H,m),4.32(2H,s);

[0371] 19 F NMR(CDCl3)δ:-137.4(1F,d),-148.6(2F,t),-159.6(2F,m).

[0372] [Example 7]

[0373] Synthesis of N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-tetrakis(pentafluorophenyl)borate ammonium

[0374] Dissolve N,N-dioctadecyl-(2,3,4,5,6-pentafluorophenyl)methyl-1-amine hydrochloride (0.50 g, 0.68 mmol) obtained in Production Example 9 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate-tri(ethyl ether) complex (0.58 g, 0.60 mol), and stir at room temperature for 1 hour. Filter the insoluble matter, and concentrate the filtrate under reduced pressure at 45 °C to obtain the title compound (0.83 g, 98%).

[0375] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.21 - 1.30 (60H, m), 1.73 (4H, br s), 3.05 (4H, br s), 4.27 (2H, s);

[0376] 19 F NMR (CDCl3) δ: -134.1 (8H, br s), -139.8 (2H, br s), -146.0 (1H, br s), -158.5 (2H, br s), -163.6 (4H, t), -167.8 (8H, t).

[0377] Add methylcyclohexane to the compound of Example 7 to prepare a 10 wt% methylcyclohexane solution, and confirm that it is a homogeneous solution.

[0378] [Production Example 10]

[0379] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroacetamide

[0380] Dissolve dicyclohexylamine (2.0 g, 11 mmol) and triethylamine (1.2 g, 12 mmol) in tetrahydrofuran (50 mL), and add trifluoroacetic anhydride (2.3 g, 11 mmol) dropwise at room temperature. After stirring at room temperature for 1 hour, add 1 M hydrochloric acid. Extract with n-hexane, dry over anhydrous magnesium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 90 / 10) to obtain the title compound (2.65 g, 87%).

[0381] 1 H NMR (CDCl3) δ: 1.08 - 1.84 (14H, m), 2.38 - 2.48 (4H, m), 3.01 - 3.08 (2H, m), 3.65 - 3.68 (2H, m);

[0382] 19 19F NMR (CDCl3) δ: -70.3 (3F, s).

[0383] [Production Example 11]

[0384] Synthesis of N,N-Dicyclohexyl-2,2,2-trifluoroethylamine

[0385] Dissolve N,N-dicyclohexyl-2,2,2-trifluoroacetamide (2.65 g, 9.56 mmol) obtained in Production Example 10 in tetrahydrofuran (30 mL), and add a tetrahydrofuran solution (20 mL) of 1.0 M borane-tetrahydrofuran complex at room temperature. Stir the reaction mixture at 60 °C for 5 hours. Allow to cool naturally to room temperature, and carefully add dropwise water (30 mL) under ice-cooling. Extract the mixture with n-hexane, wash with saturated brine, dry over anhydrous magnesium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (2.35 g, 93%).

[0386] 1 1H NMR (CDCl3) δ: 0.87 - 1.25 (10H, m), 1.56 - 1.78 (10H, m), 2.51 - 2.57 (2H, m), 3.11 (2H, q);

[0387] 19 19F NMR (CDCl3) δ: -72.9 (3F, t).

[0388] [Production Example 12]

[0389] Synthesis of N,N-Dicyclohexyl-2,2,2-trifluoroethylamine Hydrochloride

[0390] Dissolve N,N-dicyclohexyl-2,2,2-trifluoroethylamine (2.35 g, 8.9 mmol) obtained in Production Example 1 in n-hexane (30 mL), add a 1.0 M hydrogen chloride-diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (2.65 g, 99%).

[0391] 1 1H NMR (CDCl3) δ: 1.18 - 1.40 (6H, m), 1.69 - 1.81 (6H, m), 1.95 - 2.07 (4H, m), 2.19 (4H, br s), 3.44 - 3.52 (2H, m), 3.76 (2H, q);

[0392] 19 19F NMR (CDCl3) δ: -59.7 (3F, t).

[0393] [Example 8]

[0394] Synthesis of N,N-dicyclohexyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0395] Dissolve N,N-dicyclohexyl-2,2,2-trifluoroethylamine hydrochloride (0.33 g, 1.1 mmol) obtained in Production Example 12 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate-tri(ethyl ether) complex (1.0 g, 1.1 mmol), and stir at room temperature for 1 hour. Remove insoluble matters by filtration, and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 45 °C to obtain the title compound (0.98 g, 94%).

[0396] 1 H NMR (CDCl3) δ: 1.13 - 2.06 (20H, m), 3.42 - 3.48 (2H, m), 3.66 (2H, q);

[0397] 19 F NMR (CDCl3) δ: -66.0 (3F, s), -134.0 (8H, m), -163.8 (4F, m), -167.8 (8F, m).

[0398] [Production Example 13]

[0399] Synthesis of N,N-dihexyl-2,2-difluoroethylamine

[0400] Dissolve 1-hexanal (2.5 g, 25 mmol) and 2,2-difluoroethylamine (1 g, 12 mmol) in tetrahydrofuran (30 mL), add sodium triacetoxyborohydride (6 g, 28 mmol), and stir at room temperature for 15 hours. Make the reaction mixture alkaline by adding saturated aqueous sodium hydrogen carbonate solution, and extract with diethyl ether. Wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (2.98 g, 97%).

[0401] 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.21 - 1.44 (16H, m), 2.46 - 2.50 (4H, m), 2.76 (2H, dt), 5.74 (1H, tt);

[0402] 19 F NMR (CDCl3) δ: -120.4 (2F, dt).

[0403] [Production Example 14]

[0404] Synthesis of N,N-dihexyl-2,2-difluoroethylamine hydrochloride

[0405] Dissolve N,N-dihexyl-2,2-difluoroethylamine (2.95 g, 11.8 mmol) obtained in Production Example 13 in n-hexane (30 mL), add 1.0 M hydrogen chloride - diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (3.05 g, 90%).

[0406] 1 H NMR (CDCl3) δ: 0.90 (6H, t), 1.30 - 1.41 (12H, m), 1.78 - 1.86 (4H, m), 3.07 - 3.17 (4H, m), 3.36 - 3.45 (2H, m), 6.78 (1H, tt);

[0407] 19 F NMR (CDCl3) δ: -118.3 (2H, dt).

[0408] [Example 9]

[0409] Synthesis of N,N-dihexyl-2,2-difluoroethylammonium tetrakis(pentafluorophenyl)borate

[0410] Dissolve N,N-dihexyl-2,2-difluoroethylamine hydrochloride (0.40 g, 1.4 mmol) obtained in Production Example 14 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (1.25 g, 1.38 mmol), and stir at room temperature for 1 hour. Remove the insoluble matter by filtration and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 45 °C to obtain the title compound (1.04 g, 81%).

[0411] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.24 - 1.36 (12H, m), 1.64 - 1.72 (4H, m), 3.16 - 3.21 (4H, m), 3.40 - 3.48 (2H, m), 6.18 (1H, t);

[0412] 19 F NMR (CDCl3) δ: -65.3 (2F, dt), -134.1 (8H, m), -163.4 (4F, t), -167.6 (8F, m).

[0413] [Production Example 15]

[0414] Synthesis of N,N-Dihexyl-3,3,3-trifluoropropylamine

[0415] Dissolve 1-hexanal (1 g, 10 mmol), 2,2-difluoroethylamine (0.5 g, 4.0 mmol) and acetic acid (0.3 mL) in tetrahydrofuran (30 mL), add sodium triacetoxyborohydride (2.5 g, 12 mmol), and stir at room temperature for 15 hours. Add saturated aqueous sodium bicarbonate solution to the mixture to make it alkaline, and extract with n-hexane. Wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (1.35 g, 100%).

[0416] 1 H NMR (CDCl3) δ: 0.87 - 0.92 (6H, m), 1.25 - 1.45 (16H, m), 2.16 - 2.29 (2H, m), 2.36 - 2.41 (4H, m), 2.67 - 2.71 (2H, m);

[0417] 19 F NMR (CDCl3) δ: -66.5 (3F, t).

[0418] [Production Example 16]

[0419] Synthesis of N,N-Dihexyl-3,3,3-trifluoropropylamine Hydrochloride

[0420] Dissolve the N,N-dihexyl-3,3,3-trifluoropropylamine (1.0 g, 3.55 mmol) obtained in Production Example 15 in n-hexane (30 mL), add 1.0 M hydrogen chloride - diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (1.1 g, 97%).

[0421] 1 H NMR (CDCl3) δ: 0.90 (6H, t), 1.31 - 1.39 (12H, m), 1.77 - 1.84 (4H, m), 2.87 - 2,99 (1H, m), 3.00 - 3.05 (3H, m), 3.18 (1H, m);

[0422] 19 F NMR (CDCl3) δ: -66.6 (3F, t)

[0423] [Example 10]

[0424] Synthesis of N,N-Dihexyl-3,3,3-trifluoropropylammonium Tetrakis(pentafluorophenyl)borate

[0425] N,N-Dihexyl-3,3,3-trifluoropropylamine hydrochloride (0.30 g, 0.94 mmol) obtained in Preparation Example 16 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.85 g, 0.94 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.90 g, 100%).

[0426] 1 H NMR(CDCl3)δ:0.87(6H,t),1.21-1.35(12H,m),1.63-1.69(4H,m),2.56-2.61(2H,m),3.07(4H,m),3.30-3.35(2H,m);

[0427] 19 F NMR(CDCl3)δ:-66.4(3F,t),-134.1(8F,br s),-163.4(4F,t),-167.7(8F,m).

[0428] [Production Example 17]

[0429] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylamine

[0430] 1-Octanal (1.5 g, 5.59 mmol), 2,2,3,3,3-pentafluoropropylamine (0.40 g, 2.7 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (1.2 g, 5.7 mmol) was added, and the mixture was stirred at room temperature for 15 hours. A saturated aqueous sodium bicarbonate solution was added to the mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (1.65 g, 100%).

[0431] 1 H NMR(CDCl3)δ:0.88(6H,t),1.25-1.43(64H,m),2.56(4H,br s),2.95-3.10(2H,m);

[0432] 19 F NMR(CDCl3)δ:-85.2(3F,br s),-121.2(2F,br s).

[0433] [Production Example 18]

[0434] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylamine hydrochloride

[0435] N,N-Dioctadecyl-2,2,3,3,3-pentafluoropropylamine (1.5 g, 2.29 mmol) obtained in Preparation Example 17 was dissolved in n-hexane (30 mL). 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (1.45 g, 92%).

[0436] 1 H NMR(CDCl3)δ:0.88(6H,t),1.19-1.40(64H,m),1.94(4H,br s),3.22(4H,t),3.77(2H,t);

[0437] 19 F NMR(CDCl3)δ:-86.3(3F,br s),-117.8(2H,t).

[0438] [Example 11]

[0439] Synthesis of N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylammonium tetrakis(pentafluorophenyl)borate: N,N-dioctadecyl-2,2,3,3,3-pentafluoropropylamine hydrochloride (0.50 g, 0.72 mmol) obtained in Preparation Example 18 was dissolved in chloroform (30 mL). Lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.65 g, 0.72 mmol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.89 g, 93%).

[0440] 1 H NMR(CDCl3)δ:0.88(6H,t),1.18-1.31(64H,m),1.72(4H,br s),3.21-3.23(4H,m),3.67(2H,t);

[0441] 19 F NMR(CDCl3)δ:-85.9(3F,t),-118.6(2F,m),-134.0(8F,br s),-163.4(4F,t),-167.6(8F,m).

[0442] Methylcyclohexane was added to the compound of Example 11 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0443] [Production Example 19]

[0444] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylamine

[0445] Dissolve 1-octanal (5.5 g, 43 mmol), 2,2,2-trifluoroethylamine (2.0 g, 20 mmol) and acetic acid (0.5 mL) in tetrahydrofuran (50 mL), add sodium triacetoxyborohydride (10 g, 47 mmol), and stir at room temperature for 15 hours. Add saturated aqueous sodium bicarbonate solution to the reaction mixture to make it alkaline, and extract with n-hexane. Wash the organic layer with saturated brine, dry over anhydrous sodium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (5.56 g, 85%).

[0446] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.27 - 1.43 (24H, m), 2.56 (4H, t), 3.00 (2H, q);

[0447] 19 F NMR (CDCl3) δ: -71.3 (3F, s).

[0448] [Production Example 20]

[0449] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylamine hydrochloride

[0450] Dissolve the N,N-dioctyl-2,2,2-trifluoroethylamine (1.5 g, 4.64 mmol) obtained in Production Example 19 in n-hexane (30 mL), add 1.0 M hydrogen chloride - diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (1.45 g, 87%).

[0451] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.26 - 1.34 (20H, m), 1.94 (4H, br s), 3.15 (4H, brs), 3.78 (2H, q);

[0452] 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0453] [Example 12]

[0454] Synthesis of N,N-dioctyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0455] N,N-Dioctyl-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 1.39 mmol) obtained in Preparation Example 20 was dissolved in chloroform (10 mL). Lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (1.25 g, 1.38 mmol) was added and stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.25 g, 87%).

[0456] 1 H NMR(CDCl3)δ:0.86(6H,t),1.19-1.29(20H,m),1.67-1.73(4H,m),3.18-3.22(4H,m),3.62-3.67(2H,m);

[0457] 19 F NMR(CDCl3)δ:-66.0(3F,t),-134.1(8F,br s),-163.4(4F,t),-167.6(8F,m).

[0458] [Production Example 21]

[0459] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylamine

[0460] 1-dodecanal (5.5 g, 30 mmol), 2,2,2-trifluoroethylamine (1.5 g, 15 mmol) and acetic acid (0.5 mL) were dissolved in tetrahydrofuran (50 mL), sodium triacetoxyborohydride (7 g, 33 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (6.5 g, 99%).

[0461] 1 H NMR(CDCl3)δ:0.88(6H,t),1.26-1.43(40H,m),2.56(4H,t),3.00(2H,q);

[0462] 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0463] [Production Example 22]

[0464] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylamine hydrochloride

[0465] N,N-didodecyl-2,2,2-trifluoroethylamine (0.5 g, 1.06 mmol) obtained in Preparation Example 21 was dissolved in n-hexane (30 mL), and a 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (2.09 g, 96%).

[0466] 1 H NMR(CDCl3)δ:0.87(6H,t),1.26-1.34(36H,m),1.93(4H,br s),3.15(4H,brs),3.78(2H,q);

[0467] 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0468] [Example 13]

[0469] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0470] N,N-didodecyl-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 1.06 mmol) obtained in Preparation Example 22 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.96 g, 1.06 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.19 g, 100%).

[0471] 1 H NMR(CDCl3)δ:0.87(6H,t),1.19-1.29(36H,m),1.65-1.71(4H,m),3.15-3.22(4H,m),3.65(2H,q);

[0472] 19 F NMR(CDCl3)δ:-66.4(3F,br s),-134.0(8F,m),-163.4(4F,t),-167.6(8F,m).

[0473] Methylcyclohexane was added to the compound of Example 13 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0474] [Production Example 23]

[0475] Synthesis of N,N-Dioctadecyl-2,2-difluoroethylamine

[0476] 1-Octadecanal (3.0 g, 11 mmol), 2,2-difluoroethylamine (0.45 g, 5.6 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.50 g, 12 mmol) was added. The mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate was added to the reaction mixture to make it alkaline, and extraction was carried out with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (2.9 g, 89%).

[0477] 1 H NMR (CDCl3) δ: 0.89 (6H, t), 1.17 - 1.47 (64H, m), 2.49 (4H, t), 2.77 (2H, dt), 5.75 (1H, t);

[0478] 19 F NMR (CDCl3) δ: -120.4 (2H, dt).

[0479] [Production Example 24]

[0480] Synthesis of N,N-Dioctadecyl-2,2-difluoroethylamine Hydrochloride

[0481] The N,N-dioctadecyl-2,2-difluoroethylamine (2.0 g, 3.41 mmol) obtained in Production Example 23 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride - diethyl ether solution (20 mL) was added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (2.09 g, 98%).

[0482] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18 - 1.41 (58H, m), 1.79 - 1.83 (4H, m), 3.07 - 3.11 (4H, m), 3.32 - 3.38 (4H, m), 6.78 (1H, t);

[0483] 19 F NMR (CDCl3) δ: -118.2 (2F, dt).

[0484] [Example 14]

[0485] Synthesis of N,N-Dioctadecyl-2,2-difluoroethylammonium Tetrakis(pentafluorophenyl)borate

[0486] N,N-Dioctadecyl-2,2-difluoroethylamine hydrochloride (0.50 g, 0.80 mmol) obtained in Preparation Example 24 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.72 g, 0.79 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (0.97 g, 97%).

[0487] 1 H NMR(CDCl3)δ:0.86(3H,t),1.17-1.43(58H,m),1.71(4H,br s),3.16(4H,brs),3.42(2H,t),6.25(1H,t);

[0488] 19 F NMR(CDCl3)δ:-121.3(2F,d),-134.0(8F,d),-163.4(8F,t),-167.6(8F,t).

[0489] Methylcyclohexane was added to the compound of Example 14 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0490] [Production Example 25]

[0491] Synthesis of 1-(2,2,2-trifluoroethyl)piperidine hydrochloride

[0492] 1-(2,2,2-Trifluoroethyl)piperidine (1.5 g, 8.97 mmol) was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride-diethyl ether solution (20 mL) was added, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (1.85 g, 100%).

[0493] 1 H NMR(CDCl3)δ:1.43-1.94(4H,m),2.37(2H,br s),3.10(2H,br s),3.56(2H,brs),3.77(2H,t);

[0494] 19 F NMR (CDCl3) δ: -63.0 (3F, t).

[0495] [Example 15]

[0496] Synthesis of 1-(2,2,2-trifluoroethyl)piperidinium tetrakis(pentafluorophenyl)borate

[0497] 1-(2,2,2-Trifluoroethyl)piperidine hydrochloride (0.30 g, 1.47 mmol) obtained in Preparation Example 25 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (1.33 g, 1.46 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 45°C to obtain the title compound (1.19 g, 96%).

[0498] 1 H NMR(CDCl3)δ:1.47-1.62(2H,m),1.92-1.99(2H,m),2.10-2.20(2H,m),3.01(2H,br s),3.57-3.63(4H,m);

[0499] 19 F NMR(CDCl3)δ:-63.2(3F,t),-134.0(8F,br s),-163.8(4F,t),-167.9(8F,m).

[0500] [Production Example 26]

[0501] Synthesis of N,N-dioctadecyl-3,3,3-trifluoropropylamine

[0502] 1-Octanal (2.4 g, 8.94 mmol), 3,3,3-trifluoropropylamine (0.50 g, 4.42 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (2.10 g, 9.9 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (2.4 g, 88%).

[0503] 1 H NMR(CDCl3)δ:0.88(6H,t),1.18-1.43(64H,m),2.23-2.27(2H,m),2.38-2.44(4H,m),2.70(2H,t);

[0504] 19 F NMR (CDCl3) δ: -66.5 (3F, t).

[0505] [Production Example 27]

[0506] Synthesis of N,N - dioctadecyl - 3,3,3 - trifluoropropylamine hydrochloride

[0507] Dissolve N,N - dioctadecyl - 3,3,3 - trifluoropropylamine (1.5 g, 2.43 mmol) obtained in Production Example 26 in n - hexane (10 mL), add 1.0 M hydrogen chloride - diethyl ether solution (10 mL), and stir for 3 hours. Filter the precipitated precipitate, wash with n - hexane, and dry under reduced pressure to obtain the title compound (1.45 g, 91%).

[0508] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19 - 1.40 (60H, m), 1.70 - 1.81 (4H, m), 2.86 - 3.03 (6H, m), 3.17 - 3.22 (2H, m);

[0509] 19 F NMR (CDCl3) δ: - 66.6 (3F, t).

[0510] [Example 16]

[0511] Synthesis of N,N - dioctadecyl - 3,3,3 - trifluoropropyltetrakis(pentafluorophenyl)borate ammonium

[0512] Dissolve N,N - dioctadecyl - 3,3,3 - trifluoropropylamine hydrochloride (0.50 g, 0.764 mmol) obtained in Production Example 27 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (0.65 g, 0.72 mmol), and stir at room temperature for 1 hour. Remove the insoluble matter by filtration, and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 70 °C to obtain the title compound (0.89 g, 96%).

[0513] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18 - 1.38 (60H, m), 1.65 - 1.72 (4H, m), 2.60 - 2.67 (2H, m), 3.04 - 3.07 (4H, m), 3.27 - 3.32 (2H, m);

[0514] 19 F NMR (CDCl3) δ: - 64.4 (3F, t), - 131.8 (8F, m), - 161.4 (4F, m), - 165.6 (8F, m).

[0515] Add methylcyclohexane to the compound of Example 16 to prepare a 10 wt% methylcyclohexane solution, and confirm that it is a homogeneous solution.

[0516] [Production Example 28]

[0517] Synthesis of N,N-dioctadecyl-2-fluoroethylamine

[0518] 1-Octadecanal (3.0 g, 11 mmol), a tert-butanol solution of 2-fluoroethylamine (10 wt%, 3.3 g, 5.2 mmol), and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), and sodium triacetoxyborohydride (2.50 g, 12 mmol) was added. The mixture was stirred at room temperature for 15 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture to make it alkaline, and extraction was performed with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 90 / 10) to obtain the title compound (2.02 g, 32%).

[0519] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.18 - 1.64 (65H, m), 2.44 - 2.51 (4H, m), 2.77 (2H, dt), 4.50 (1H, dt);

[0520] 19 F NMR (CDCl3) δ: -2220.6 (1F, br s).

[0521] [Production Example 29]

[0522] Synthesis of N,N-dioctadecyl-2-fluoroethylamine hydrochloride

[0523] The N,N-dioctadecyl-2-fluoroethylamine (1.50 g, 2.64 mmol) obtained in Production Example 28 was dissolved in n-hexane (30 mL), and 1.0 M hydrogen chloride - diethyl ether solution (20 mL) was added, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (1.45 g, 91%).

[0524] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19 - 1.40 (60H, m), 1.78 - 1.82 (4H, m), 3.04 - 3,11 (4H, m), 3.32 - 3.40 (2H, m), 5.02 (2H, dt);

[0525] 19 F NMR (CDCl3) δ: -223.5 (1F, m).

[0526] [Example 17]

[0527] Synthesis of N,N-dioctadecyl-2-fluoroethyltetrakis(pentafluorophenyl)ammonium borate

[0528] N,N-Dioctadecyl-2-fluoroethylamine hydrochloride (0.50 g, 0.83 mmol) obtained in Preparation Example 29 was dissolved in chloroform (30 mL), and lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (0.75 g, 0.83 mmol) was added. The mixture was stirred at room temperature for 1 hour. Insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 70°C to obtain the title compound (0.89 g, 86%).

[0529] 1 H NMR(CDCl3)δ:0.88(6H,t),1.18-1.31(60H,m),1.65-1.73(4H,m),3.11-3.13(4H,m),3.34-3.43(2H,m),4.76(2H,dt);

[0530] 19 F NMR(CDCl3)δ:-133.9(8F,br s),-163.3(4F,t),-167.5(8F,m),-223.4(1H,brs).

[0531] Methylcyclohexane was added to the compound of Example 17 to prepare a 10 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0532] [Production Example 30]

[0533] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazine

[0534] To a solution of 1,4-bis(trifluoroacetyl)piperazine (3.5 g, 13 mmol) in tetrahydrofuran (30 mL) was added a 1 M solution of a borane-tetrahydrofuran complex in tetrahydrofuran (40 mL, 40 mmol) at room temperature, followed by stirring at 60°C for 3 hours. The mixture was ice-cooled, water was carefully added, and then extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5-80 / 20) to obtain the title compound (2.08 g, 66%).

[0535] 1 H NMR(CDCl3)δ:2.71(8H,s),2.96(4H,q);

[0536] 19 F NMR (CDCl3) δ: -70.2 (6F, t).

[0537] [Production Example 31]

[0538] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazine dihydrochloride

[0539] Dissolve 1,4-bis(2,2,2-trifluoroethyl)piperazine (1.50 g, 6.0 mmol) obtained in Production Example 30 in n-hexane (30 mL), add 1.0 M hydrogen chloride-diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the mixture under reduced pressure to obtain the title compound (1.85 g, 96%).

[0540] 1 H NMR (DMSO-d6) δ: 3.03 (8H, br s), 3.67 (4H, br s);

[0541] 19 F NMR (DMSO-d6) δ: -65.8 (6F, br s).

[0542] [Example 18]

[0543] Synthesis of 1,4-bis(2,2,2-trifluoroethyl)piperazinium bis[tetrakis(pentafluorophenyl)borate]

[0544] Dissolve 1,4-bis(2,2,2-trifluoroethyl)piperazine dihydrochloride (0.50 g, 1.55 mmol) obtained in Production Example 31 in dichloromethane (50 mL), add lithium tetrakis(pentafluorophenyl)borate-tris(diethyl ether) complex (2.81 g, 3.09 mmol), and stir at room temperature for 3 hours. Filter the insoluble matter, dissolve it in water and dichloromethane, and separate the organic layer. Dry the organic layer with anhydrous magnesium sulfate and concentrate it under reduced pressure to obtain the title compound (0.87 g, 35%).

[0545] 1 H NMR (DMSO-d6) δ: 2.78 (8H, br s), 3.93 (4H, br s);

[0546] 19 F NMR (DMSO-d6) δ: -67.6 (6F, br s), -132.7 (16F, br s), -161.6 (8F, t), -166.2 (16F, t).

[0547] [Production Example 32]

[0548] Synthesis of N,N-didodecyl-2,2,2-trifluoroethylamine

[0549] 1-Dodecaldehyde (4.0 g, 12.3 mmol), 2,2,2-trifluoroethylamine (0.50 g, 5.0 mmol) and acetic acid (0.05 mL) were dissolved in tetrahydrofuran (50 mL), sodium triacetoxyborohydride (2.80 g, 13 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (1.38 g, 40%).

[0550] 1 H NMR(CDCl3)δ:0.88(6H,t),1.25-1.30(76H,m),1.40-1.43(4H,m),2.56(4H,t),3.00(2H,q);

[0551] 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0552] [Production Example 33]

[0553] Synthesis of N,N-didocosyl-2,2,2-trifluoroethylamine hydrochloride

[0554] N,N-didocosyl-2,2,2-trifluoroethylamine (1.30 g, 1.82 mmol) obtained in Preparation Example 32 was dissolved in n-hexane (30 mL), and a 1.0 M hydrogen chloride-diethyl ether solution (10 mL) was added, followed by stirring for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain the title compound (1.34 g, 98%).

[0555] 1 H NMR(CDCl3)δ:0.88(6H,t),1.25-1.40(76H,m),1.85-2.00(4H,m),3.14(4H,t),3.75(2H,q);

[0556] 19 F NMR (CDCl3) δ: -63.5 (3F, t).

[0557] [Example 19]

[0558] Synthesis of N,N-didocosyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0559] N,N-bis(didodecyl)-2,2,2-trifluoroethylamine hydrochloride (0.40 g, 0.53 mmol), lithium tetrakis(pentafluorophenyl)borate - mono(diethyl ether) complex (0.41 g, 0.53 mmol) and methylcyclohexane (20 mL) were mixed and stirred at room temperature for 3 hours. After washing the reaction mixture with water, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 45 °C to obtain the title compound (0.65 g, 88%).

[0560] 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.25 - 1.29 (76H, m), 1.60 - 1.65 (4H, m), 3.12 - 3.16 (4H, m), 3.60 (2H, q);

[0561] 19 F NMR (CDCl3) δ: -65.9 (3F, t), -132.8 (8F, t), -162.3 (4F, m), -166.2 (8F, m).

[0562] Methylcyclohexane was added to the compound of Example 19 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed to be a homogeneous solution.

[0563] [Production Example 34]

[0564] Synthesis of N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine

[0565] 3,7,11,15-Tetramethylhexadecanal (2.3 g, 7.8 mmol), 2,2,2-trifluoroethylamine (0.20 g, 2.0 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (1.5 g, 7.8 mmol) was added, and the mixture was stirred at room temperature for 15 hours. The reaction mixture was made basic by adding saturated aqueous sodium bicarbonate solution and extracted with n-hexane. After washing the organic layer with saturated brine, it was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (1.13 g, 85%).

[0566] 1 H NMR (CDCl3) δ: 0.84 - 0.88 (30H, m), 1.07 - 1.56 (48H, m), 2.57 - 2.61 (4H, m), 3.00 (2H, q);

[0567] 1919F NMR (CDCl3) δ: -70.9 (3F, t).

[0568] [Production Example 35]

[0569] Synthesis of N,N-(3,7,11,15-Tetramethylhexadecyl)-2,2,2-trifluoroethylamine Hydrochloride

[0570] Dissolve N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine (2.35 g, 3.56 mmol) obtained in Production Example 34 in n-hexane (20 mL), add 1.0 M hydrogen chloride-diethyl ether solution (10 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (2.48 g, 100%).

[0571] 1 1H NMR (CDCl3) δ: 0.84 - 0.95 (30H, m), 1.13 - 1.57 (48H, m), 3.13 - 3.25 (4H, m), 3.76 (2H, q);

[0572] 19 19F NMR (CDCl3) δ: -63.4 (3F, t).

[0573] [Example 20]

[0574] Synthesis of N,N-(3,7,11,15-Tetramethylhexadecyl)-2,2,2-trifluoroethylammonium Tetrakis(pentafluorophenyl)borate

[0575] Mix N,N-(3,7,11,15-tetramethylhexadecyl)-2,2,2-trifluoroethylamine hydrochloride (0.50 g, 0.72 mmol), lithium tetrakis(pentafluorophenyl)borate-tri(ethyl ether) complex (0.66 g, 0.72 mmol) and methylcyclohexane (15 mL), and stir at room temperature for 3 hours. Wash the mixture with water, dry the organic layer with anhydrous magnesium sulfate, and concentrate under reduced pressure at 45 °C to obtain the title compound (0.96 g, 68%).

[0576] 1 1H NMR (CDCl3) δ: 0.82 - 0.89 (30H, m), 1.13 - 1.57 (48H, m), 3.15 - 3.25 (4H, m), 3.60 (2H, q);

[0577] 19 19F NMR (CDCl3) δ: -67.1 (3F, t), -133.9 (8F, d), -164.4 (4F, t), -167.5 (8F, t).

[0578] Methylcyclohexane was added to the compound of Example 20 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed to be a homogeneous solution.

[0579] [Production Example 36]

[0580] Synthesis of N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylamine

[0581] 3,7,11-Trimethyldodecanal (1.2 g, 5.3 mmol), 2,2,2-trifluoroethylamine (0.20 g, 2.0 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (1.5 g, 7.8 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Aqueous saturated sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and extraction was carried out with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0 - 95 / 5) to obtain the title compound (0.95 g, 91%).

[0582] 1 H NMR (CDCl3) δ: 0.83 - 0.88 (24H, m), 1.00 - 1.57 (34H, m), 2.58 - 2.60 (4H, m), 3.00 (2H, q);

[0583] 19 F NMR (CDCl3) δ: -71.1 (3F, t).

[0584] [Example 21]

[0585] Synthesis of N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0586] The N,N-(3,7,11-trimethyldodecyl)-2,2,2-trifluoroethylamine (0.56 g, 1 mmol) obtained in Production Example 36 was dissolved in methylcyclohexane (20 mL), 1.0 M hydrogen chloride - diethyl ether solution (1 mL) was added, and lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (0.91 g, 1 mmol) was added. The reaction mixture was stirred at room temperature for 1 hour. The mixture was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and concentrated at 45 °C under reduced pressure to obtain the title compound (1.20 g, 74%).

[0587] 11H NMR (CDCl3) δ: 0.81 - 0.89 (24H, m), 1.03 - 1.51 (34H, m), 2.95 - 3.00 (4H, m), 3.41 (2H, q);

[0588] 19 19F NMR (CDCl3) δ: -68.2 (3F, t), -133.9 (8F, d), -164.4 (4F, t), -167.5 (8F, t).

[0589] Methylcyclohexane was added to the compound of Example 21 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed to be a homogeneous solution.

[0590] [Example 22]

[0591] Production of a composition containing ammonium bis(octadecyl)-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)borate and bis(octadecyl)-2,2,2-trifluoroethylamine

[0592] Bis(octadecyl)-2,2,2-trifluoroethylamine (0.90 g, 1.49 mmol) obtained in Production Example 2 was dissolved in chloroform (30 mL), lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (0.91 g, 1.00 mmol) and 1.0 M hydrogen chloride - diethyl ether solution were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was dried under reduced pressure at 70 °C to obtain the title composition (1.51 g).

[0593] 1 1H NMR (CDCl3) δ: 0.86 (6H, t), 1.23 - 1.30 (60H, m), 1.68 - 1.76 (4H, m), 3.12 - 3.16 (4H, m), 3.61 (2H, q);

[0594] 19 19F NMR (CDCl3) δ: -65.3 (4.8F, t), -133.9 (8F, m), -163.8 (4F, t), -167.8 (8F, t).

[0595] n-Hexane was added to the composition of Example 22 to prepare a 20 wt% n-hexane solution, and it was confirmed to be a homogeneous solution.

[0596] Isohexane was added to the composition of Example 22 to prepare a 20 wt% isohexane solution, and it was confirmed to be a homogeneous solution.

[0597] n-heptane was added to the composition of Example 22 to prepare a 20 wt% n-heptane solution, which was confirmed to be a homogeneous solution.

[0598] ISOPAR E (registered trademark) was added to the composition of Example 22 to prepare a 20 wt % ISOPAR E (registered trademark) solution, which was then confirmed to be a homogeneous solution.

[0599] Cyclohexane was added to the composition of Example 22 to prepare a 20 wt% cyclohexane solution, which was confirmed to be a uniform solution.

[0600] Methylcyclohexane was added to the composition of Example 22 to prepare a 20 wt % methylcyclohexane solution, which was confirmed to be a uniform solution.

[0601] [Production Example 37]

[0602] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylamine

[0603] 1-Tetradecanal (4.0 g, 18.8 mmol), 2,2,2-trifluoroethylamine (0.90 g, 9.1 mmol) and acetic acid (0.3 mL) were dissolved in tetrahydrofuran (30 mL), sodium triacetoxyborohydride (4.0 g, 18.9 mmol) was added, and the mixture was stirred at room temperature for 15 hours. Saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (4.0 g, 89%).

[0604] 1 H NMR(CDCl3)δ:0.88(6H,t),1.26-1.43(48H,m),2.55(4H,t),3.00(2H,q);

[0605] 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0606] [Production Example 38]

[0607] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylamine hydrochloride

[0608] Dissolve N,N-ditetradecyl-2,2,2-trifluoroethylamine (1.50 g, 3.05 mmol) obtained in Production Example 37 in n-hexane (30 mL), add 1.0 M hydrogen chloride-diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (1.45 g, 90%).

[0609] 1 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.20 - 1.40 (44H, m), 1.96 (4H, br s), 3.15 (4H, br s), 3.78 (2H, q);

[0610] 19 19F NMR (CDCl3) δ: -63.4 (3F, t).

[0611] [Example 23]

[0612] Synthesis of N,N-ditetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate

[0613] Dissolve N,N-ditetradecyl-2,2,2-trifluoroethylamine (0.60 g, 1.14 mmol) obtained in Production Example 38 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate-tri(ethyl ether) complex (1.04 g, 1.14 mmol), and stir at room temperature for 1 hour. Remove the insoluble matter by filtration, and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 70 °C to obtain the title compound (1.34 g, 100%).

[0614] 1 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.19 - 1.36 (44H, m), 1.65 - 1.70 (4H, m), 3.14 - 3.18 (4H, m), 3.62 (2H, q);

[0615] 19 19F NMR (CDCl3) δ: -66.4 (3F, t), -134.0 (8F, m), -163.4 (4F, t), -167.6 (8F, t).

[0616] Add cyclohexane to Example 23 to prepare a 20 wt% cyclohexane solution, and confirm that it is a homogeneous solution.

[0617] [Example 24]

[0618] Production of a composition containing N,N-ditetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and didodecyl ether

[0619] N,N-Di-tetradecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (58 mg, 0.05 mmol) obtained in Example 23 and didodecyl ether (40 mg, 0.10 mmol) were added and mixed to obtain the title composition.

[0620] 1 H NMR(CDCl3)δ:0.85-0.88(18H,m),1.24-1.35(116H,m),1.51-1.58(8H,m),1.64-1.70(4H,m),3.11-3.15(4H,m),3.38(8H,t),3.60(2H,q);

[0621] 19 F NMR(CDCl3)δ:-66.6(3F,s),-134.0(8F,s),-163.5(4F,t),-167.6(8F,t).

[0622] N-hexane was added to the composition of Example 24 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0623] [Production Example 39]

[0624] Synthesis of N,N-dihexadecyl-2,2,2-trifluoroethylamine

[0625] 1-Hexadecanal (4.0 g, 16.6 mmol), 2,2,2-trifluoroethylamine (0.84 g, 8.5 mmol) and acetic acid (0.5 mL) were dissolved in tetrahydrofuran (50 mL), sodium triacetoxyborohydride (4.0 g, 18.9 mmol) was added, and the mixture was stirred at room temperature for 15 hours. A saturated aqueous sodium bicarbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted with n-hexane. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 100 / 0-95 / 5) to obtain the title compound (4.56 g, 98%).

[0626] 1 H NMR(CDCl3)δ:0.88(6H,t),1.26-1.43(56H,m),2.56(4H,t),3.00(2H,q);

[0627] 19 F NMR (CDCl3) δ: -71.3 (3F, t).

[0628] [Production Example 40]

[0629] Synthesis of N,N-Dihexadecyl-2,2,2-trifluoroethylamine Hydrochloride

[0630] Dissolve N,N-dihexadecyl-2,2,2-trifluoroethylamine (1.50 g, 2.74 mmol) obtained in Production Example 39 in n-hexane (30 mL), add 1.0 M hydrogen chloride - diethyl ether solution (20 mL), and stir for 1 hour. Concentrate the reaction mixture under reduced pressure to obtain the title compound (1.55 g, 97%).

[0631] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19 - 1.40 (52H, m), 1.93 (4H, br s), 3.15 (4H, br s), 3.77 (2H, q);

[0632] 19 F NMR (CDCl3) δ: -63.4 (3F, t).

[0633] [Example 25]

[0634] Synthesis of N,N-Dihexadecyl-2,2,2-trifluoroethylammonium Tetrakis(pentafluorophenyl)borate

[0635] Dissolve N,N-dihexadecyl-2,2,2-trifluoroethylamine (0.60 g, 1.03 mmol) obtained in Production Example 40 in chloroform (30 mL), add lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (0.95 g, 1.05 mmol), and stir at room temperature for 1 hour. Remove the insoluble matter by filtration and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 70 °C to obtain the title compound (1.51 g).

[0636] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.19 - 1.36 (54H, m), 1.65 - 1.70 (4H, m), 3.14 - 3.18 (4H, m), 3.62 (2H, q);

[0637] 19 F NMR (CDCl3) δ: -66.4 (3F, t), -134.0 (8F, m), -163.4 (4F, t), -167.6 (8F, t).

[0638] Add cyclohexane to the compound of Example 25 to prepare a 20 wt% cyclohexane solution, and confirm that it is a homogeneous solution.

[0639] [Example 26]

[0640] Preparation of a composition containing N,N-dihexadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)ammonium borate and dihexadecyl ether

[0641] N,N-Dihexadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (60 mg, 0.05 mmol) and dicetyl ether (23 mg, 0.05 mmol) obtained in Example 25 were added and mixed to obtain the title composition.

[0642] 1 H NMR(CDCl3)δ:0.86-0.90(12H,m),1.20-1.36(104H,m),1.52-1.58(4H,m),1.63-1.70(4H,m),3.15-3.19(4H,m),3.39(4H,t),3.64(2H,q);

[0643] 19 F NMR(CDCl3)δ:-66.7(3F,s),-134.1(8F,s),-163.5(4F,t),-167.6(8F,t).

[0644] N-hexane was added to the composition of Example 26 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0645] [Example 27]

[0646] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and dioctyl ether

[0647] N,N-Dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) and dioctyl ether (12 mg, 0.05 mmol) obtained in Example 1 were added and mixed to obtain the title composition.

[0648] 1 H NMR(CDCl3)δ:0.88(12H,t),1.20-1.37(80H,m),1.52-1.58(4H,m),1.65-1.70(4H,m),3.14-3.19(4H,m),3.39(4H,t),3.63(2H,q);

[0649] 19 F NMR(CDCl3)δ:-66.6(3F,br s),-134.0(8F,br s),-163.4(4F,t),-167.6(8F,t).

[0650] n-Hexane was added to the composition of Example 27 to prepare a 20 wt% n-hexane solution, and it was confirmed to be a homogeneous solution.

[0651] [Example 28]

[0652] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)borate and didodecyl ether

[0653] N,N-Dioctadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) and didodecyl ether (15 mg, 0.05 mmol) obtained in Example 1 were added and mixed to obtain the title composition.

[0654] 1 H NMR (CDCl3) δ: 0.86 - 0.90 (12H, m), 1.20 - 1.38 (96H, m), 1.53 - 1.60 (4H, m), 1.65 - 1.72 (4H, m), 3.15 - 3.20 (4H, m), 3.39 (4H, t), 3.65 (2H, q);

[0655] 19 F NMR (CDCl3) δ: -66.4 (3F, br s), -134.0 (8F, br s), -163.4 (4F, t), -167.5 (8F, m).

[0656] n-Hexane was added to the composition of Example 28 to prepare a 20 wt% n-hexane solution, and it was confirmed to be a homogeneous solution.

[0657] [Example 29]

[0658] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)borate and distearyl ether

[0659] N,N-Dioctadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) and distearyl ether (23 mg, 0.05 mmol) obtained in Example 1 were added and mixed to obtain the title composition.

[0660] 1 H NMR (CDCl3) δ: 0.86 - 0.98, (12H, m), 1.20 - 1.35 (112H, m), 1.52 - 1.75 (8H, m), 3.15 - 3.20 (4H, m), 3.39 (4H, t), 3.65 (2H, q);

[0661] 19F NMR(CDCl3)δ:-66.5(3F,br s),-134.2(8F,br s),-163.6(4F,t),-167.7(8F,m).

[0662] N-hexane was added to the composition of Example 29 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0663] [Example 30]

[0664] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and diphenyl ether

[0665] N,N-Dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) obtained in Example 1 and diphenyl ether (8.5 mg, 0.05 mmol) were added and mixed to obtain the title composition.

[0666] 1 H NMR(CDCl3)δ:0.86-0.90,(6H,m),1.20-1.40(58H,m),1.62-1.68(4H,m),3.12-3 .16(4H,m),3.61(4H,q),6.99-7.03(4H,m),7.08-7.12(2H,m),7.31-7.36(4H,m);

[0667] 19 F NMR(CDCl3)δ:-66.9(3F,br s),-134.1(8F,br s),-163.4(4F,t),-167.6(8F,m).

[0668] N-hexane was added to the composition of Example 30 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0669] [Example 31]

[0670] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and octadecylphenyl ether

[0671] N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) and octadecylphenyl ether (18 mg, 0.05 mmol) obtained in Example 1 were added and mixed to obtain the title composition.

[0672] 1H NMR(CDCl3)δ:0.84-0.98(12H,m),1.20-1.44(85H,m),1.62-1.81(6H,m),3.13 -3.18(4H,m),3.61(4H,q),3.95(2H,t),6.88-6.94(2H,m),7.25-7.30(3H,m);

[0673] 19 F NMR(CDCl3)δ:-66.8(3F,br s),-134.1(8F,br s),-163.4(4F,t),-167.6(8F,m).

[0674] N-hexane was added to the composition of Example 31 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0675] [Example 32]

[0676] Production of a composition containing N,N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate and cyclopentyl methyl ether

[0677] N,N-Dioctadecyl-2,2,2-trifluoroethylammonium tetrakis(pentafluorophenyl)borate (64 mg, 0.05 mmol) and cyclopentyl methyl ether (10 mg, 0.10 mmol) obtained in Example 1 were added and mixed to obtain the title composition.

[0678] 1 H NMR(CDCl3)δ:0.88(6H,t),1.20-1.35(60H,m),1.53-1.56(4H,m),1.61-1. 76(16H,m),3.12-3.17(4H,m),3.28(6H,s),3.61(2H,q),3.79-3.83(2H,m);

[0679] 19 F NMR(CDCl3)δ:-66.6(3F,br s),-133.9(8F,br s),-163.5(4F,t),-167.6(8F,m).

[0680] N-hexane was added to the composition of Example 32 to prepare a 20 wt % n-hexane solution, which was confirmed to be a uniform solution.

[0681] [Example 33]

[0682] Preparation of a composition containing N,N-dihexadecyl-2,2,2-trifluoroethyltetrakis(pentafluorophenyl)ammonium borate and ditetradecyl ether

[0683] Dissolve N,N - bis(hexadecyl)-2,2,2 - trifluoroethylamine hydrochloride (8.10 g, 13.9 mmol) obtained in Production Example 40 in dichloromethane (80 mL), add ditetradecyl ether (8.10 g, 13.9 mmol) and lithium tetrakis(pentafluorophenyl)borate - tris(diethyl ether) complex (14.2 g, 13.7 mmol), and stir at room temperature for 1 hour. Add water to the reaction mixture, stir at room temperature for 1 hour, then separate the aqueous layer, and wash the organic layer with water. Dry the organic layer over anhydrous sodium sulfate, then filter, and concentrate the filtrate under reduced pressure. Dry the residue under reduced pressure at 80 °C to obtain the title composition (22.5 g).

[0684] 1 H NMR (CDCl3) δ: 0.87 - 0.89 (12H, m), 1.20 - 1.80 (104H, m), 3.21 - 3.24 (4H, m), 3.38 - 3.41 (4H, m), 3.69 (2H, q);

[0685] 19 F NMR (CDCl3) δ: - 66.7 (3F, br s), - 134.0 (8F, m), - 163.4 (4F, t), - 167.5 (8F, t).

[0686] Add n - hexane to the composition obtained in Example 33 to prepare a 20 wt% n - hexane solution, and confirm that it is a homogeneous solution.

[0687] [Example 34]

[0688] Production of a composition containing N,N - bis(hexadecyl)-2,2,2 - trifluoroethylammonium tetrakis(pentafluorophenyl)borate and didodecyl ether

[0689] Mix N,N - bis(hexadecyl)-2,2,2 - trifluoroethylammonium tetrakis(pentafluorophenyl)borate (439.2 mg, 0.36 mmol) obtained in Example 25 with didodecyl ether (254 mg, 0.72 mmol), and add n - hexane (1.756 g) to prepare a homogeneous hexane solution of the title composition. Confirm that the solution is homogeneous. Concentrate this solution under reduced pressure and analyze it by NMR.

[0690] 1 H NMR (CDCl3) δ: 0.87 - 0.91 (12H, m), 1.20 - 1.42 (100H, m), 1.53 - 1.69 (12H, m), 3.20 - 3.24 (4H, m), 3.40 (8H, t), 3.67 (2H, q);

[0691] 19 19F NMR (CDCl3) δ: -66.9 (3F, t), -134.0 (8F, m), -163.8 (4F, t), -167.4 (8F, t).

[0692] [Comparative Example 1]

[0693] An attempt was made to prepare a 10 wt% methylcyclohexane solution or a 10 wt% n - hexane solution of N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate, but a homogeneous solution could not be obtained. In the test examples described later, N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate was used as the cocatalyst in Comparative Example 1.

[0694] [Comparative Example 2]

[0695] An attempt was made to prepare a 10 wt% n - hexane solution of N,N - dioctadecyl - methylammonium tetrakis(pentafluorophenyl)borate, but a homogeneous solution could not be obtained. In the test examples described later, N,N - dioctadecyl - methylammonium tetrakis(pentafluorophenyl)borate was used as the cocatalyst in Comparative Example 2.

[0696] [Test Example] (Polymerization Performance Evaluation)

[0697] The following shows a general polymerization method using the compound or composition of the present invention as a cocatalyst.

[0698] In a glove box, 1 - octene, triisobutylaluminum (TIBA, 0.55 M hexane solution), and a solvent (methylcyclohexane (MCH) or toluene) were added to a 100 mL autoclave to prepare a comonomer solution. A polymerization catalyst, dimethylsilylene(tert - butylamido)(tetramethylcyclopentadienyl) - titanium(IV) - dichloride (CGC), triisobutylaluminum (0.55 M hexane solution), and a solvent were added to prepare a catalyst solution with a predetermined concentration, which was then transferred to a Schlenk flask. The cocatalyst was dissolved in a solvent to prepare a cocatalyst solution with a predetermined concentration, which was then transferred to a Schlenk flask. During the reaction after mixing the comonomer solution, catalyst solution, and cocatalyst solution, preparation was carried out in such a way that the total amount of the solvent and the total amount of triisobutylaluminum were constant. After purging the autoclave with ethylene, the catalyst solution and the cocatalyst solution were sequentially added to the autoclave, and immediately the ethylene pressure was adjusted to a predetermined pressure. Stirring was carried out for a predetermined time at a predetermined temperature (25 °C or 100 °C). After cooling the reaction mixture, the ethylene gas was removed, and then the mixture was poured into methanol (100 mL) containing 3 mL of hydrochloric acid and stirred at room temperature for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60 °C to obtain an ethylene - octene copolymer.

[0699] [Melting Point Measurement]

[0700] The measurement based on differential scanning calorimetry (DSC) was carried out using a DSC6220 machine (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.

[0701] Hereinafter, the results of the polymerization reaction at 25 °C or 100 °C are shown in Table 1 and Table 2, respectively.

[0702] [Table 1]

[0703]

[0704] Reaction conditions: catalyst: CGC; catalyst: cocatalyst = 1:1; TIBA (total amount 3000 μmol);

[0705] Total amount of solvent (40 mL); 1-octene (1 mL); ethylene pressure (8 atmospheres); 25 °C.

[0706] [Table 2]

[0707]

[0708] Reaction conditions: catalyst: CGC; catalyst: cocatalyst = 1:1; TIBA (total amount 100 μmol);

[0709] Total amount of solvent (40 mL); 1-octene (1 mL); ethylene pressure (8 atmospheres); 100 °C.

[0710] It can be confirmed from Table 1 and Table 2 that: regardless of the polymerization temperature and the type of solvent used, the ammonium fluoroborate compounds of Examples 1, 2, 4, 7, 11, and 22 all show higher polymerization activity than the compounds of Comparative Example 1 and Comparative Example 2 without fluorine atoms. Furthermore, as shown in Table 1, it can be considered that: the composition (or complex) of the present invention (Examples 1, 2, 4, and 22) can obtain a polymer with a lower melting point than that of the comparative example according to the polymerization conditions, and the introduction amount of the comonomer increases.

[0711] Industrial applicability

[0712] The compound or composition of the present invention shows high metal complex catalyst activation ability in the polymerization reaction of olefins, dienes, and acetylenes, and is useful as a cocatalyst. In addition, according to the present invention, an industrial production method of the compound or composition of the present invention can also be provided.

[0713] This application is based on Japanese Patent Application No. 2020-144177 filed in Japan on August 28, 2020, Japanese Patent Application No. 2020-196704 filed on November 27, 2020, and Japanese Patent Application No. 2021-037078 filed on March 9, 2021, and all of their contents are incorporated herein by reference.

Claims

1. A compound represented by the following formula (1), In formula (1), R 1 、R 2 、R 3 and R 4 each independently represents a C 1-4 aryl substituted with one or more fluorine atoms or one or more fluorinated C 6-14 alkyl groups, R 5 represents fluoro C 1-6 alkyl R 6 and R 7 each independently represents a C 1-30 alkyl group optionally substituted by a halogen atom n represents 1, m represents 1, and R 5 、R 6 and R 7 have a total carbon atom count of 25 or more.

2. The compound according to claim 1, wherein, R 1 、R 2 、R 3 and R 4 each independently is phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 9-phenanthryl or 3-phenanthryl, each of which is substituted by one or more fluorine atoms or one or more fluorinated C 1-4 alkyl groups.

3. The compound according to claim 1, wherein R 1 、R 2 、R 3 and R 4 are each a pentafluorophenyl group, a 2,2’,3,3’,4’,5,5’,6,6’-nonafluoro-4-(1,1’-biphenyl) 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.

4. A composition comprising the compound according to any one of claims 1 to 3 and a compound represented by the following formula (2), In formula (2), R and R' each independently represent an optionally substituted C 1-30 alkyl group, an optionally substituted C 3-15 cycloalkyl group or an optionally substituted C 6-14 aryl group.

5. The composition according to claim 4, wherein, R and R' are each independently optionally substituted C 1-30 alkyl groups.

6. The composition according to claim 4 or 5, wherein, The content of the compound represented by formula (2) is in the range of 0.01 to 10 moles relative to 1 mole of the compound represented by formula (1).

7. The composition according to claim 4 or 5, wherein The content of the compound represented by formula (2) is in the range of 0.1 to 3 moles relative to 1 mole of the compound represented by formula (1).

8. A composition comprising the compound according to any one of claims 1 to 3 and a compound represented by the following formula (3), wherein, In this composition, the compound represented by formula (3) is an amine compound obtained by deprotonating the cation constituting formula (1) of claim 1, In formula (3), R 5 represents a fluoro C 1-6 alkyl group, R 6 and R 7 each independently represents a C 1-30 alkyl group optionally substituted by a halogen atom.

9. The composition according to claim 8, wherein, The content of the compound represented by formula (3) is in the range of 0.01 to 10 moles relative to 1 mole of the compound represented by formula (1).

10. The composition according to claim 8, wherein, The content of the compound represented by formula (3) is in the range of 0.5 to 3 moles relative to 1 mole of the compound represented by formula (1).

11. The composition according to any one of claims 8 to 10, further comprising a compound represented by the following formula (2), In formula (2), R and R' each independently represent optionally substituted C 1-30 alkyl, optionally substituted C 3-15 cycloalkyl or optionally substituted C 6-14 aryl.

12. A cocatalyst for the polymerization of at least one monomer selected from the group consisting of olefins and acetylene, the cocatalyst comprising the compound according to any one of claims 1 to 3 or the composition according to any one of claims 4 to 11.

13. A method for manufacturing a polymer, comprising: Using the compound according to any one of claims 1 to 3 or the composition according to any one of claims 4 to 11 as a cocatalyst to polymerize at least one monomer selected from the group consisting of olefins and acetylene.

14. A method for producing a compound represented by the following formula (1), In formula (1), R 1 、R 2 、R 3 and R 4 each independently represents a C 1-4 aryl substituted by one or more fluorine atoms or one or more fluorinated C 6-14 alkyl groups, R 5 represents fluoro C 1-6 alkyl, R 6 and R 7 each independently represents a C 1-30 alkyl group optionally substituted by a halogen atom n represents 1, m represents 1, and R 5 , R 6 and R 7 have a total carbon atom number of 25 or more, The manufacturing method is characterized in that it includes: A step of reacting a compound represented by the following formula (4) with a compound represented by the following formula (3) in the presence of a protonic acid, In formula (4), R 1 、R 2 、R 3 and R 4 represent the same meanings as the definitions of the respective groups in the above formula (1), M p+ represents an alkali metal ion or an alkaline earth metal ion, and p represents 1 or 2, R in formula (3) 5 , R 6 and R 7 represent the same meanings as the definitions of the respective groups in formula (1) above.

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