Novel borate compounds

Abstract

The object of this invention is to provide borate compounds useful as cocatalysts for the polymerization of olefins and dienes. This invention relates to borate compounds represented by the following formula (1) and their use as cocatalysts for the polymerization of olefins and dienes. [The symbols in the formula are defined as described in the specification.]

Description

Technical Field

[0001] This invention relates to borate compounds useful as cocatalysts for the polymerization of olefins and dienes, and methods for their production. Background Technology

[0002] For a long time, there have been numerous reports on the use of non-metallocene metal complex catalysts, such as metallocene compounds, diimine complexes, and phenoxy complexes, as catalysts for the polymerization of olefins and dienes. As co-catalysts used to stabilize the cationic active species of these metal complex catalysts, aluminum oxanes (MAO) such as alkylaluminum and methylaluminoxane; Brønsted salts such as ammonium borate; and Lewis salts such as triphenylcarbomonium borate (Non-Patent Literature 1).

[0003] In the aforementioned catalytic activation reaction of Brønsted acid salts, the leaving group on the metal complex catalyst is protonated and detaches from the metal complex catalyst, generating a cationic active species of the metal complex catalyst. Thus, the noncoordinate anion derived from the Brønsted acid salt stabilizes the active species. Various borate compounds, such as tetra(pentafluorophenyl)borate, have been reported as Brønsted bases constituting this Brønsted acid salt (Non-Patent Document 1), and Brønsted acids containing nitrogen, phosphorus, oxygen, and / or sulfur are known (Patent Document 1).

[0004] As Brønsted salts mentioned above, known examples include nitrogen-containing Brønsted salts (ammonium borates) such as dimethylaniline tetra(pentafluorophenyl)borate, tris(n-butyl)ammonium tetra(pentafluorophenyl)borate, and methylpyrrolidineonium tetra(pentafluorophenyl)borate (Patent Document 2). In catalytic activation reactions based on these ammonium borates, amine compounds are generated by losing protons during the protonation stage. These amine compounds may interact with the cationic active species of the metal complex catalyst, which raises concerns about adverse effects on the polymerization reaction.

[0005] Furthermore, non-polar hydrocarbon solvents are used as solvents in the polymerization process. In particular, from the viewpoint of odor and toxicity, aliphatic hydrocarbon solvents such as n-hexane are being gradually replaced compared to aromatic hydrocarbon solvents such as toluene.

[0006] However, it is known that: typical tetra(pentafluorophenyl)borate compounds are poorly soluble in aromatic hydrocarbon solvents such as toluene, or even if they are dissolved, they will separate into a liquid-liquid two-phase mixture consisting of a thick phase containing dissolved borate compounds and a thin phase containing undissolved borate compounds (Patent Document 3).

[0007] Furthermore, since tetra(pentafluorophenyl)borate compounds are poorly soluble in aliphatic hydrocarbon solvents such as n-hexane and n-heptane, compounds soluble in aliphatic hydrocarbon solvents are desired and proposed (Patent Document 4). The di(octadecyl)methylammonium tetra(pentafluorophenyl)borate and bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate described in Patent Document 4 are useful as compounds soluble in hydrocarbon solvents.

[0008] However, when using the di(octadecyl)methylammonium tetra(pentafluorophenyl)borate and bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate described in Patent Document 4, the trialkylamine generated after the catalytic activation reaction is nucleophilic. Therefore, there is concern that it may become a catalyst poison for the polymerization reaction of olefins and dienes.

[0009] Existing technical documents

[0010] Non-patent literature

[0011] Non-patent literature 1: Chem. Rev. 2000, 100, 1391-1434

[0012] Patent documents

[0013] Patent Document 1: US Patent No. 5,132,380

[0014] Patent Document 2: International Publication No. 2010 / 014344

[0015] Patent Document 3: Japanese Patent Application Publication No. 2018-104335

[0016] Patent Document 4: Japanese Patent Publication No. 2000-507157 Summary of the Invention

[0017] The problem the invention aims to solve

[0018] In view of these prior art, the present invention provides borate compounds that are soluble in hydrocarbon solvents and useful as co-catalysts for the polymerization of olefins and dienes, and their industrial preparation methods.

[0019] Solution for solving the problem

[0020] Through in-depth research, the inventors first discovered that the compound represented by the following formula (1) (hereinafter also referred to as "the compound of the present invention") does not produce a compound that would become a catalyst poison for the polymerization reaction of olefins and dienes, and is useful as a co-catalyst for the polymerization reaction of olefins and dienes, and thus completed the present invention.

[0021]

[0022] [In the formula, R] 1 R2 R 3 and R 4 Each independently represents a substance containing one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl-substituted C 6-14 Aryl,

[0023] [A + -H] indicates that it is composed of two or more identical or different Cs. 1-30 Alkyl groups or two or more identical or different carbon atoms 1-30 A cation obtained by protonation of the cyclic nitrogen atom of a five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compound with alkoxy-substituted carbon atoms and a total carbon number of 25 or more.

[0024] That is, the present invention is as follows.

[0025] [1] A compound represented by the following formula (1).

[0026]

[0027] [In the formula, R] 1 R 2 R 3 and R 4 Each independently represents a substance containing one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl-substituted C 6-14 Aryl,

[0028] [A + -H] indicates that it is composed of two or more identical or different Cs. 1-30 Alkyl groups or two or more identical or different carbon atoms 1-30 A cation obtained by protonation of the cyclic nitrogen atom of a five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compound with alkoxy-substituted carbon atoms and a total carbon number of 25 or more.

[0029] [2] According to the compound described in [1] above, wherein R 1 R 2 R 3 and R 4 Each of the following is independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups: phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 9-phenanthyl, or 3-phenanthyl.

[0030] [3] According to the compound described in [1] above, wherein R 1 R 2 R 3 and R 4All are 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.

[0031] [4] The compound according to any one of [1] to [3] above, wherein A is composed of two identical or different C atoms. 9-30 Alkyl groups or two identical or different carbon atoms 9-30 Alkoxy-substituted, five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds with a total carbon number of 25 or more.

[0032] [5] According to the compound described above [4], the five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compound is pyridine or imidazole.

[0033] [6] A polymerization cocatalyst for a monomer, wherein the polymerization cocatalyst comprises any one of the compounds described in any one of [1] to [5] above, and the monomer is at least one selected from the group consisting of olefins and dienes.

[0034] [7] A method for manufacturing a polymer, comprising: using the compound described in any one of [1] to [5] above as a co-catalyst, and polymerizing at least one monomer selected from the group consisting of olefins and dienes.

[0035] The effects of the invention

[0036] According to the present invention, the aforementioned borate compound is capable of being soluble in hydrocarbon solvents and useful as a co-catalyst for the polymerization of olefins and dienes. Detailed Implementation

[0037] The following explains the definitions of the terms and symbols used in this specification.

[0038] In this specification, "halogen atom" refers to a fluorine atom, chlorine atom, bromine atom, or iodine atom.

[0039] In this specification, "alkyl" refers to an alkyl group that has one or more carbon atoms and is either straight-chain or branched.

[0040] In this instruction manual, "C" 1-30"Alkyl" refers to alkyl groups with 1 to 30 carbon atoms in a straight or branched chain. Examples 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, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, etc.

[0041] In this instruction manual, "C" 9-30 "Alkyl" refers to alkyl groups with 9 to 30 carbon atoms in a straight or branched chain. Examples include nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hexadecyl, nonadecanyl, triadecyl, etc.

[0042] In this instruction manual, "C" 1-6 "Alkyl" refers to alkyl groups with 1 to 6 carbon atoms, whether straight-chain or branched. Examples 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. Preferably, C16 is used. 1-4 alkyl.

[0043] In this instruction manual, "halogenated C" 1-6 "Alkyl" refers to the aforementioned "C" 1-6 A group in which one or more hydrogen atoms of an alkyl group are replaced by a halogen. Specifically, examples include difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl, etc. Among these, a halogenated group is preferred. 1-4 alkyl".

[0044] In this instruction manual, "fluorine C" 1-6 "Alkyl" refers to the aforementioned "halogenated C" 1-6The halogen atom in the "alkyl" group is a fluorine atom. Specifically, examples include difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, and 6,6,6-trifluorohexyl. Among these, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, and 4,4,4-trifluorobutyl are preferred. 1-4 "Alkyl", more preferably difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, and particularly preferably trifluoromethyl.

[0045] In this specification, "cycloalkyl" refers to a cyclic alkyl group, and unless otherwise specified, it is preferably C10. 3-8 Cycloalkyl.

[0046] In this instruction manual, "C" 3-8 "Cycloalkyl" refers to cyclic alkyl groups with 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Preferably, it has 3 carbon atoms. 3-6 Cycloalkyl.

[0047] In this specification, "alkoxy(group)" refers to a group obtained by bonding a straight-chain or branched alkyl group with an oxygen atom.

[0048] In this instruction manual, "C" 1-30 "Alkoxy" refers to alkoxy groups with 1 to 30 carbon atoms in their straight or branched chains. Examples 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, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, nonadecanyloxy, eicosyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, octadecyloxy, nonadecanyloxy, triadecyloxy, etc.

[0049] In this instruction manual, "C" 9-30"Alkoxy" refers to alkoxy groups with 9 to 30 carbon atoms in their straight or branched chains. Examples include nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, hexadecoxy, octadecoxy, nonadecanoxy, eicosoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, hexadecoxy, octadecoxy, nonadecanoxy, triadecoxy, etc.

[0050] In this instruction manual, "C" 1-6 "Alkoxy" refers to an alkoxy group with 1 to 6 carbon atoms in its straight or branched chain. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, and hexoxy. Preferably, it contains C4 atoms. 1-4 Alkyl group.

[0051] In this instruction manual, "halogenated C" 1-6 "Alkoxy(group)" refers to the aforementioned "C 1-6 The "alkoxy" group is a group in which one or more hydrogen atoms are replaced by halogen atoms. Specifically, examples include difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, 5,5,5-trifluoropentoxy, and 6,6,6-trifluorohexyloxy. Among these, "halogenated C" is preferred. 1-4 Alkyl groups.

[0052] In this instruction manual, "fluorine 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, examples include difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, 5,5,5-trifluoropentoxy, and 6,6,6-trifluorohexyloxy. Among these, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3,3,3-trifluoropropoxy, and 4,4,4-trifluorobutoxy are preferred. 1-4 "Alkoxy(group)" is more preferably difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy or pentafluoroethoxy, and particularly preferably trifluoromethoxy.

[0053] In this specification, "aromatic" refers to a monocyclic or polycyclic (fused) hydrocarbon group that exhibits aromaticity. Specifically, examples include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 3-phenanthyl, 9-phenanthyl, etc. 6-14 Aryl group. Preferably, it is phenyl, 1-naphthyl, or 2-naphthyl.

[0054] In this specification, "five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds" refers to five- or six-membered monocyclic aromatic heterocyclic compounds that, in addition to carbon atoms, contain 1 to 4 heteroatoms selected from nitrogen, sulfur, and oxygen atoms, and that contain at least one nitrogen atom as a cyclic atom.

[0055] Suitable examples of the "five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compound" include, for example, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetraazole, triazine, etc., wherein pyridine or imidazole is more preferred.

[0056] In this specification, "optionally substituted" means unsubstituted or having one or more substituents. Unless otherwise specified, the following can be listed as "substituents": (1) halogen atom, (2) nitro group, (3) cyano group, (4) C 1-30 Alkyl, (5) halogenated C 1-6 Alkyl, (6)C 3-8 cycloalkyl, (7)C 1-30 Alkoxy, (8) halogenated C 1-6 Alkoxy, (9)C 6-14 Aryl groups, etc. Preferably, the halogen atom, cyano group, or C group is present. 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy, halogenated C 1-6 alkoxy or phenyl, more preferably a halogen atom (e.g., a fluorine atom), C 1-6 Alkyl (e.g., methyl, ethyl), C 1-6 Alkyl groups (e.g., methoxy, ethoxy) or halogenated C 1-6 Alkyl groups (e.g., trifluoromethyl). Furthermore, in the presence of multiple substituents, the substituents may optionally be the same or different. Additionally, the aforementioned substituents may optionally be further substituted with one or more carbon atoms. 1-6 Alkyl group, one or more carbon atoms 1-6 Substitution with alkoxy groups, one or more halogen atoms, one or more phenyl groups, etc.

[0057] In this specification, "hydrocarbon solvent" refers to a solvent containing aromatic hydrocarbon solvents and / or aliphatic hydrocarbon solvents. From the viewpoint of odor and toxicity, aliphatic hydrocarbon solvents are preferred.

[0058] In this specification, examples of "aromatic hydrocarbon solvents" include benzene, toluene, and xylene.

[0059] In this specification, examples of "aliphatic hydrocarbon solvents" include n-hexane, isohexane, heptane, octane, cyclohexane, methylcyclohexane, and mixtures thereof.

[0060] In this specification, "soluble in hydrocarbon solvents" means that at 25°C, in a solution of hydrocarbon solvent and the compound of the present invention, the compound of the present invention dissolves at a concentration of 5% by weight or more to form a transparent and homogeneous solution.

[0061] (The compounds of this invention)

[0062] The compounds of the present invention will now be described.

[0063] The compounds of the present invention are those represented by the following formula (1).

[0064]

[0065] [In the formula, R] 1 R 2 R 3 and R 4 Each independently represents a substance containing one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl-substituted C 6-14 Aryl,

[0066] [A + -H] indicates that it is composed of two or more identical or different Cs. 1-30 Alkyl groups or two or more identical or different carbon atoms 1-30 A cation obtained by protonation of the cyclic nitrogen atom of a five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compound with alkoxy-substituted carbon atoms and a total carbon number of 25 or more.

[0067] The following explains the preferred method for option A.

[0068] As A, it is preferably represented by two identical or different Cs. 9-30 Alkyl groups or two identical or different carbon atoms 9-30Alkoxylated, five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds (e.g., pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetraazole, triazine, etc.), more preferably substituted with the same or different two C atoms. 14-30 Alkyl groups or two identical or different carbon atoms 14-30 Alkoxy-substituted pyridines or imidazoles.

[0069] In addition, the total number of carbon atoms in A is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more.

[0070] Preferred specific examples of A include, for example, 2,5-bis(nonadecanyl)pyridine, 2,6-bis(nonadecanyl)pyridine, 2-nonadecanyl-5-octadecylpyridine, 2-nonadecanyl-4-octadecyloxypyridine, 2-nonadecanyl-6-octadecyloxypyridine, 4-nonadecanyl-1-octadecylimidazole, 5-nonadecanyl-1-octadecylimidazole, 2-nonadecanyl-1-octadecylimidazole, etc.

[0071] (A is matched by two or more identical or different Cs) 1-30 Alkyl groups or two or more identical or different carbon atoms 1-30 Method for manufacturing alkoxy-substituted, five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds with a total carbon number of 25 or more.

[0072] Regarding the aforementioned A, as shown in the following formula, the phosphonium salt (R) is reacted in a solvent that will not affect the reaction and in the presence of a base. 5 -CH2PPh3X') reacts with compound (a1) to obtain compound (a2) (step 1), and A can be produced by reacting with a reducing agent (step 2).

[0073]

[0074] (In the formula, the following formula)

[0075]

[0076] The groups shown represent five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic groups; X' represents a halogen atom; R 5 Indicates that C is arbitrarily replaced. 1-30 Alkyl group; n1 represents an integer greater than or equal to 2.

[0077] Examples of alkalis used in step 1 include sodium hydride, potassium carbonate, and potassium tert-butoxide.

[0078] The amount of base used is 1 to 2 moles (preferably 1 to 1.2 moles) relative to the equivalent (1 mole) of the formyl group of compound (a1).

[0079] The phosphonium salt used (R) 5 The amount of -CH2PPh3X') relative to the formyl group of compound (a1) is also 1 to 2 moles (preferably 1 to 1.2 moles).

[0080] The reaction solvent for step 1 is not particularly limited. For example, it is preferred to use ether solvents such as tetrahydrofuran and diethoxyethane; aromatic hydrocarbon solvents such as toluene; aliphatic hydrocarbon solvents such as n-hexane; dimethylformamide, dimethyl sulfoxide, etc.

[0081] The preferred reaction temperature for step 1 is room temperature to 180°C.

[0082] The reaction time for process 1 is typically 0.5 hours to 48 hours.

[0083] In step 2 described above, hydrogen, ammonium formate, ammonium chloride, etc., can be used as reducing agents in the presence of a metal catalyst. Pd / C, Pt / C, or other transition metal catalysts are preferred as the metal catalyst.

[0084] The amount of metal catalyst used is 0.001 to 1.0 moles (preferably 0.01 to 0.5 moles) relative to the double bond equivalent (1 mole) of compound (a2).

[0085] The reaction solvent for step 2 is not particularly limited, but is preferably n-hexane, toluene, tetrahydrofuran, ethanol, etc., and a mixture thereof can be used.

[0086] The reduction reaction in step 2 can be carried out under appropriate conditions such as normal pressure or medium pressure, depending on the progress of the reaction.

[0087] The preferred reaction temperature for step 2 is room temperature to 180°C.

[0088] The reaction time for step 2 is typically 1 hour to 72 hours.

[0089] Hereinafter, a preferred embodiment of the compound represented by the aforementioned formula (1) (hereinafter also referred to as "compound (1)") will be described.

[0090] The following describes each group of compound (1).

[0091] R 1 R 2 R 3 and R 4 Preferably, each is independently surrounded by one or more fluorine atoms or one or more fluorine carbon atoms. 1-4Alkyl (e.g., trifluoromethyl) substituted, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 3-phenanthyl, or 9-phenanthyl, more preferably each independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups, phenyl, 1-naphthyl, or 2-naphthyl, particularly preferred R 1 R 2 R 3 and R 4 All of them 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.

[0092] A cation derived from A, namely [AH] + The preferred method for A in this context is the same as described above.

[0093] The following compounds can be listed as suitable compounds (1).

[0094] [Compound (1-1)]

[0095] A compound (1), wherein, in the aforementioned formula (1),

[0096] R 1 R 2 R 3 and R 4 Each is independently formed by one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl (e.g., trifluoromethyl) substituted, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 3-phenanthyl or 9-phenanthyl;

[0097] A is defined by two or more identical or different Cs. 9-30 Alkyl groups or two or more identical or different carbon atoms 9-30 Alkoxylated, five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds (e.g., pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetraazole, triazine, etc.); and

[0098] The total number of carbon atoms in the compound (1) is 25 or more (preferably 30 or more).

[0099] [Compounds (1-2)]

[0100] A compound (1), wherein, in the aforementioned formula (1),

[0101] R 1 R 2 R 3 and R 4 Each of the following is independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups: phenyl, 1-naphthyl, or 2-naphthyl.

[0102] A is two identical or different Cs 14-30 Alkyl groups or two identical or different carbon atoms 14-30 Alkoxy-substituted, pyridine, or imidazole (preferably 2,5-bis(nonadecanyl)pyridine, 2,6-bis(nonadecanyl)pyridine, 2-nonadecanyl-5-octadecylpyridine, 2-nonadecanyl-4-octadecyloxypyridine, 2-nonadecanyl-6-octadecyloxypyridine, 4-nonadecanyl-1-octadecylimidazol, 5-nonadecanyl-1-octadecylimidazol, or 2-nonadecanyl-1-octadecylimidazol); and

[0103] The total number of carbon atoms in the compound (1) is 35 or more.

[0104] [Compounds (1-3)]

[0105] A compound (1), wherein, in the aforementioned formula (1),

[0106] R 1 R 2 R 3 and R 4 All of them 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 (preferably pentafluorophenyl);

[0107] A is two identical or different Cs 14-30 Alkyl groups or two identical or different carbon atoms 14-30 Alkoxy-substituted pyridines (preferably 2,5-bis(nonadecanyl)pyridine, 2,6-bis(nonadecanyl)pyridine, 2-nonadecanyl-5-octadecylpyridine, 2-nonadecanyl-4-octadecyloxypyridine, or 2-nonadecanyl-6-octadecyloxypyridine); and

[0108] The total number of carbon atoms in the compound (1) is 35 or more.

[0109] Preferred examples of compound (1) include, for example, 2,6-bis(nonadecanyl)pyridinium tetra(pentafluorophenyl)borate, 2-nonadecanyl-5-octadecyloxypyridinium tetra(pentafluorophenyl)borate, 4-nonadecanyl-1-octadecylimidazolium tetra(pentafluorophenyl)borate, 5-nonadecanyl-1-octadecylimidazolium tetra(pentafluorophenyl)borate, 2-nonadecanyl-1-octadecylimidazolium tetra(pentafluorophenyl)borate, etc.

[0110] The compounds of the present invention are soluble in hydrocarbon solvents at room temperature (15-30°C). Furthermore, while conventional borate-type cocatalysts are insoluble in aliphatic hydrocarbon solvents such as n-hexane, the compounds of the present invention also exhibit solubility in aliphatic hydrocarbon solvents. Therefore, they are useful as cocatalysts for the polymerization of olefins and dienes in homogeneous systems.

[0111] (Method for manufacturing the compound of the present invention)

[0112] Hereinafter, a method for manufacturing the compound of the present invention (hereinafter also referred to as "the manufacturing method of the present invention") will be described.

[0113] The compounds of the present invention preferably do not contain metal salts (e.g., lithium tetra(pentafluorophenyl)borate) of the hydrogen borate compound shown in formula (3) described later, which may form complexes with ether compounds having a total carbon number of 7 or less and thus become catalyst poisons. Furthermore, the compositions of the present invention preferably do not contain ether compounds having a total carbon number of 7 or less that may become catalyst poisons. "Does not contain ether compounds having a total carbon number of 7 or less" means: [The text abruptly ends here, so the translation stops as well.] 1 The H-NMR analysis results showed that no ether compounds with a total carbon number of less than 7 were detected.

[0114] The manufacturing method of the present invention is characterized by a step of reacting the hydroborate compound (hereinafter also referred to as "compound (3)") shown in the following formula (3) with the aforementioned A, and using an equimolar amount (1 to 1.01 moles, preferably 1 mole) of A relative to 1 mole of compound (3).

[0115]

[0116] R in the formula 1 R 2 R 3 and R 4 The definition is the same as the one mentioned above.

[0117] In this manufacturing method, the compound (3) used as a raw material can be listed as a known compound such as tetra(pentafluorophenyl)borate, tetra(nonafluoro[1,1'-biphenyl]-4-yl)borate, tetra(heptafluoro-2-naphthyl)borate, and [3,5-bis(trifluoromethyl)phenyl]borate.

[0118] There are no particular limitations on the method of manufacturing compound (3), and examples include, for instance, the method of treating the compound shown in formula (4) (hereinafter also referred to as "compound (4)") with a protic acid.

[0119]

[0120] [In the formula, R] 1 R 2 R 3 and R 4 Each independently represents a substance containing one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl-substituted C 6-14 Aryl,

[0121] M represents alkali metals such as lithium, potassium, and sodium, or alkaline earth metals such as calcium, magnesium, and barium, and

[0122] n represents 1 or 2.

[0123] The aforementioned compound (4) used to manufacture compound (3) can be a commercially available product, a purified product, or a compound prepared by a method known to them (e.g., see Angew. Chem. Int. Ed., 2009, 48(40), 7444-7447).

[0124] There are no particular limitations on the solvents used in the manufacture of compound (3), but ideally, ether solvents such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and diisopropyl ether are preferred; halogen solvents such as dichloromethane and chloroform are preferred; aromatic hydrocarbon solvents such as toluene and benzene are preferred; and aliphatic hydrocarbon solvents such as n-hexane, isohexane, heptane, octane, cyclohexane, and methylcyclohexane are preferred. Furthermore, these solvents can be used alone or in combination.

[0125] In addition, there are no particular limitations on the protic acid used in the treatment of compound (4), and examples include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, etc.

[0126] Ideally, the amount of protic acid used to manufacture compound (3) should be an equimolar amount (1 to 1.01 moles, preferably 1 mole) relative to 1 mole of compound (4). When using more than 1 mole of protic acid, it is preferable to wash the organic phase with water until the pH of the aqueous phase after washing is 3 or higher, so that no protic acid used remains in the treated organic phase. If the pH of the aqueous phase is less than 3, the protic acid salt used remains in the organic phase, and in the subsequent reaction with A, the protic acid salt of A is generated and remains in the composition of the present invention, which is a concern as it may become a catalyst poison during polymerization.

[0127] In this manufacturing method, the solution of compound (3) prepared as described above can be directly used in the reaction with A.

[0128] As A used in the manufacturing method of the present invention, examples include five- or six-membered monocyclic nitrogen-containing aromatic heterocyclic compounds with a total carbon number of 25 or more (preferably 30 or more, more preferably 35 or more). Specific examples of A include, for example, 2,5-bis(nonadecanyl)pyridine, 2,6-bis(nonadecanyl)pyridine, 2-nonadecanyl-5-octadecylpyridine, 2-nonadecanyl-4-octadecyloxypyridine, 2-nonadecanyl-6-octadecyloxypyridine, 4-nonadecanyl-1-octadecylimidazole, 5-nonadecanyl-1-octadecylimidazole, 2-nonadecanyl-1-octadecylimidazole, etc.

[0129] Among them, compound (3) is used with C having two or more (preferably two) C 9-30 Alkyl (preferably C) 14-30 alkyl) or C 9-30 Alkoxy groups (preferably C) 14-30 Compound (1) obtained by reacting alkoxy groups with A having a total carbon number of 25 or more can also be soluble in hydrocarbon solvents.

[0130] The reaction temperature and time in the manufacturing method of the present invention are not particularly limited. The reaction temperature is usually 0°C to 40°C, preferably 10°C to 35°C, more preferably room temperature (15°C to 30°C), and the time is 10 minutes or more.

[0131] After the reaction of compound (3) with the aforementioned A is completed, the solvent is removed by dehydrating the reaction solution with anhydrous sodium sulfate, anhydrous magnesium sulfate and other drying agents, thereby obtaining compound (1).

[0132] Alternatively, as another method, a solution of compound (1) can be obtained by distilling off a portion of the reaction solvent after the reaction of compound (3) with the aforementioned A is completed, or by diluting the solvent and removing it by distillation (solvent displacement) once or multiple times.

[0133] The preferred manner of the aforementioned compound (3) is in accordance with the preferred manner of the anionic portion of the aforementioned compound (1) (the anionic portions of compounds (1-1) to (1-3)).

[0134] Alternatively, as another method, a solution of compound (1) can also be obtained by pre-preparing a salt of the aforementioned A and a protic acid (e.g., the hydrochloride salt of A), mixing an equimolar amount of the salt with compound (4) in a solvent and stirring.

[0135] In other methods, the types of protic acids and solvents, reaction temperatures, reaction times, etc., shall conform to the manufacturing method of the present invention described above.

[0136] The following compounds can be listed as suitable compounds (4).

[0137] [Compound (4-1)]

[0138] A compound (4), wherein, in the aforementioned formula (4),

[0139] R 1 R 2 R 3 and R 4 Each is independently formed by one or more fluorine atoms or one or more fluorine carbon atoms. 1-4 Alkyl (e.g., trifluoromethyl) substituted, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 3-phenanthyl or 9-phenanthyl;

[0140] M is lithium, sodium, potassium, calcium, magnesium, or barium; and

[0141] n is 1 or 2.

[0142] [Compound (4-2)]

[0143] A compound (4), wherein, in the aforementioned formula (4),

[0144] R 1 R 2 R 3 and R 4 Each of the following is independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups: phenyl, 1-naphthyl, or 2-naphthyl.

[0145] M is lithium, sodium, or potassium; and

[0146] n is 1.

[0147] [Compound (4-3)]

[0148] A compound (4), wherein, in the aforementioned formula (4),

[0149] R 1 R 2 R 3 and R 4 All of them 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;

[0150] M is either lithium or sodium; and

[0151] n is 1.

[0152] Preferred examples of compound (4) include, for example, lithium tetra(pentafluorophenyl)borate, sodium tetra(pentafluorophenyl)borate, lithium tetra(nonafluoro[1,1'-biphenyl]-4-yl)borate, lithium tetra(heptafluoro-2-naphthyl)borate, lithium [3,5-bis(trifluoromethyl)phenyl]borate, sodium [3,5-bis(trifluoromethyl)phenyl]borate, lithium tetra(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borate, lithium tetra(1,3,4,5,6,7,8-heptafluoro-2-naphthyl)borate, sodium tetra(2,3,4,5,6,7,8-heptafluoro-1-naphthyl)borate, and other known compounds.

[0153] The compounds of the present invention are soluble in hydrocarbon solvents and do not contain basic and highly nucleophilic amine compounds, their protic acid salts, ether compounds with a total carbon number of 7 or less, or other compounds that could become catalyst poisons. Therefore, they are useful as co-catalysts for the polymerization of olefins and dienes.

[0154] The present invention includes a method for manufacturing a polymer, comprising: using the compound of the present invention as a co-catalyst to polymerize at least one monomer selected from the group consisting of olefins and dienes.

[0155] Specifically, the manufacture of polymers in which the compounds of the present invention are used as co-catalysts can be carried out according to, for example, the methods described in the experimental examples described later.

[0156] Example

[0157] The present invention will be specifically illustrated through the following manufacturing examples and embodiments, but the present invention is not limited to these manufacturing examples and embodiments. Regarding yield, % means mol / mol%, and for other parameters, unless otherwise specified, % means weight%. In addition, room temperature means a temperature of 15°C to 30°C unless otherwise specified.

[0158] It should be noted that the following equipment was used during the analysis.

[0159] 1 H-NMR and 19 F-NMR: 400YH manufactured by Japan Electronics Corporation (JEOL)

[0160] In addition, the solvents and reagents used in the following examples were purchased from Sigma Aldrich, Tokyo Chemical Industry Co., Ltd., Fujifilm and Kogyo Pure Chemicals Co., Ltd., Pure Chemical Industries, Ltd., Kanto Chemical Co., Ltd., Combi-Blocks Co., Ltd., unless otherwise specified. The deuterated solvent used in the NMR determination was purchased from Cambridge Isotope Laboratories.

[0161] [Manufacturing Example 1]

[0162] Synthesis of 2,6-bis(nonadecan-1-enyl)pyridine

[0163] Potassium tert-butoxide (2.0 g, 18 mmol) was added to a mixture of pyridine-2,6-dicarboxaldehyde (1.0 g, 7.4 mmol), octadecyltriphenylphosphonium bromide (10 g, 17 mmol), and tetrahydrofuran (100 mL) at room temperature. The mixture was stirred at 60 °C for 2 hours and allowed to cool naturally to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with saturated saline solution, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting residue was suspended in diethyl ether, and the insoluble matter was filtered off. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2~90 / 10) to give 2,6-bis(nhodec-1-enyl)pyridine (E / Z mixture; 3.9 g, 86%).

[0164] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.20-1.48 (60H, m), 2.56-2.62 (4H, m), 5.82-5.89 (1H, m), 6.42-6.49 (2H, m), 7.04 (2H, d), 7.26-7.35 (1H, m), 7.53-7.57 (1H, m).

[0165] [Manufacturing Example 2]

[0166] Synthesis of 2,6-bis(nonadecanyl)pyridine

[0167] Under a hydrogen atmosphere, a mixture of 2,6-bis(nonadecano-1-enyl)pyridine (E / Z mixture; 3.5 g, 5.8 mmol), 10% Pd / C (50% aqueous content; 0.70 g), and tetrahydrofuran (100 mL) obtained in Preparation Example 1 was stirred at room temperature and atmospheric pressure for 15 hours. After filtering the mixture, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to obtain 2,6-bis(nonadecanoyl)pyridine (3.0 g, 85%).

[0168] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.17-1.40 (64H, m), 1.65-1.70 (4H, m), 2.72-2.76 (4H, m), 6.93 (2H, d), 7.48 (1H, t).

[0169] [Manufacturing Example 3]

[0170] Synthesis of 2,6-Di(nonadecanyl)pyridine hydrochloride

[0171] At room temperature, a 1M solution of diethyl ether hydrogen chloride (10 mL) was added to a hexane solution (3.0 g, 4.9 mmol) of 2,6-bis(nonadecanyl)pyridine obtained in Preparation Example 2, and the mixture was stirred for 1 hour. The resulting precipitate was filtered off, washed with hexane, and dried under reduced pressure to obtain 2,6-bis(nonadecanyl)pyridine hydrochloride (3.0 g, 94%).

[0172] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.24-1.45 (64H, m), 1.79-1.87 (4H, m), 3.32 (4H, br), 7.41 (2H, d), 8.08 (1H, br).

[0173] [Example 1]

[0174] 2,6-Di(nonadecanyl)pyridinium tetra(pentafluorophenyl)borate

[0175] The 2,6-bis(nonadecanyl)pyridine hydrochloride (0.50 g, 0.77 mmol) obtained in Preparation Example 3 and the monodiethyl ether complex of lithium tetra(pentafluorophenyl)borate (0.59 g, 0.78 mmol) were suspended in dichloromethane (20 mL) and stirred at room temperature for 1 hour. The resulting suspension was filtered and the filtrate was concentrated under reduced pressure at 50 °C to obtain 2,6-bis(nonadecanyl)pyridineonium tetra(pentafluorophenyl)borate (0.99 g, 99%).

[0176] 1 H NMR (CDCl3) δ: 0.85-0.89 (6H, m), 1.23-1.35 (64H, m), 1.72-1.76 (4H,m), 2.94-2.98 (4H, t), 7.57 (2H, d), 8.27 (1H, dd);

[0177] 19 F NMR (CDCl3) δ: -133.3 (8F, t), -163.2 (4F, t), -167.7 (8F, t).

[0178] It can be confirmed that the compound obtained in Example 1 is dissolved in methylcyclohexane at a concentration of 10% by weight.

[0179] [Manufacturing Example 4]

[0180] Synthesis of 2-(nonadecano-1-enyl)-5-octadecyloxypyridine

[0181] Potassium tert-butoxide (1.4 g, 12 mmol) was added to a mixture of 5-octadecyloxypyridine-2-carboxaldehyde (2.0 g, 5.3 mmol), octadecyltriphenylphosphonium bromide (7.0 g, 12 mmol), and tetrahydrofuran (100 mL) at room temperature. The mixture was stirred at 60 °C for 2 hours and allowed to cool naturally to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was suspended in diethyl ether, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2~90 / 10) to give 2-(nonadecano-1-enyl)-5-octadecyloxypyridine (E / Z mixture; 3.1 g, 95%).

[0182] 1H NMR (CDCl3) δ: 0.87 (6H, t), 1.24-1.50 (60H, m), 1.76-1.80 (2H, m), 2.48-2.54 (2H, m), 3.95-4.00 (2H, m), 7.71-7.78 (1H, m), 6.36-6.40 (1H, m), 7.13-7.18 (2H, m), 8.2-8.27 (1H, m).

[0183] [Manufacturing Example 5]

[0184] Synthesis of 2-nonadecanyl-5-octadecyloxypyridine

[0185] Under a hydrogen atmosphere, a mixture of 2-(nonadecano-1-enyl)-5-octadecyloxypyridine (E / Z mixture; 2.5 g, 4.1 mmol), 10% Pd / C (50% aqueous content; 0.70 g), n-hexane (100 mL), and tetrahydrofuran (100 mL) obtained in Preparation Example 4 was stirred at room temperature and atmospheric pressure for 15 hours. After filtering the reaction mixture, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to give 2-nonadecano-5-octadecyloxypyridine (1.0 g, 40%).

[0186] 1 H NMR (CDCl3) δ: 0.87 (6H, t), 1.17-1.40 (64H, m), 1.42-1.76 (4H, m), 2.67-2.72 (2H, m), 3.95 (1H, t), 7.02 (2H, d), 7.10 (2H, dd), 8.19 (1H, d).

[0187] [Manufacturing Example 6]

[0188] Synthesis of 2-nonadecanyl-5-octadecyloxypyridine hydrochloride

[0189] 1.0 M diethyl ether of hydrogen chloride (10 mL) was added to a mixture of 2-nonadecanyl-5-octadecyloxypyridine (1.0 g, 1.63 mmol) obtained in Preparation Example 5 and n-hexane (100 mL), and the mixture was stirred for 1 hour. The solvent was removed by distillation under reduced pressure to obtain the target compound (0.98 g, 93%).

[0190] 1H NMR (CDCl3) δ: 0.88 (6H, t), 1.24-1.45 (62H, m), 1.78-1.83 (4H, m), 3.14 (2H, t), 4.96 (2H, t), 7.50 (1H, d), 7.73-7.76 (1H, m), 8.20 (1H, d).

[0191] [Example 2]

[0192] Synthesis of 2-nonadecanyl-5-octadecyloxypyridinium tetra(pentafluorophenyl)borate

[0193] The 2-nonadecanyl-5-octadecyloxypyridine hydrochloride (0.25 g, 0.38 mmol) and the lithium tetra(pentafluorophenyl)borate-diethyl ether complex (0.29 g, 0.38 mmol) obtained in Preparation Example 6 were suspended in cyclohexane (50 mL) and stirred at room temperature for 1 hour. After adding brine and washing the organic phase, the mixture was dried with anhydrous magnesium sulfate and concentrated under reduced pressure. The compound described in the title was obtained by drying under reduced pressure at 45 °C (0.45 g, 90%).

[0194] 1 H NMR (CDCl3) δ: 0.86-0.90 (6H, m), 2.00-1.44 (62H, m), 1.70-1.86 (4H,m), 2.91 (2H, t), 4.04 (2H, t), 7.66 (1H, d), 7.83 (1H, d), 7.93 (1H, dd);

[0195] 19 F NMR (CDCl3) δ: -134.0 (8F, d), -163.4 (4F, t), -167.5 (8F, t).

[0196] It can be confirmed that the compound obtained in Example 2 is dissolved in methylcyclohexane at a concentration of 10% by weight.

[0197] [Manufacturing Example 7]

[0198] Synthesis of 1-octadecylimidazol-2-formaldehyde

[0199] A mixture of 1H-imidazol-2-carboxaldehyde (2.0 g, 21 mmol), 1-bromooctadecane (7.5 g, 22 mmol), potassium carbonate (4.5 g, 33 mmol), and N,N-dimethylformamide was stirred at room temperature for 15 hours. The mixture was injected into water and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (n-hexane-ethyl acetate = 98 / 2~90 / 10) to give 1-octadecylimidazol-2-carboxaldehyde (6.45 g, 89%).

[0200] 1 H NMR (CDCl3) δ: 0.88 (3H, t), 1.24-1.30 (34H, m), 1.75-1.79 (2H, m), 4.36-4.40 (2H, m), 7.15 (1H, s), 7.29 (1H, d), 9.81 (1H, s).

[0201] [Manufacturing Example 8]

[0202] Synthesis of 2-(nonadecano-1-enyl)-1-octadecylimidazol

[0203] Potassium tert-butoxide (2.0 g, 17.8 mmol) was added to a mixture of 1-octadecylimidazolium-2-carboxaldehyde (5.0 g, 14 mmol), octadecyltriphenylphosphonium bromide (10 g, 16.8 mmol), and tetrahydrofuran (50 mL) obtained in Preparation Example 7 at room temperature. The mixture was stirred at 60 °C for 2 hours and allowed to cool naturally to room temperature. The reaction mixture was carefully added to water and extracted with ethyl acetate. The organic phase was washed with a saturated saline solution, dried with anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was suspended in diethyl ether, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 98 / 2~90 / 10) to give 2-(nonadecano-1-enyl)-1-octadecylimidazolium (E / Z mixture; 7.5 g, 89%).

[0204] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.11-1.73 (64H, m), 2.20-2.26 (2H, m), 3.85-3.90 (2H, m), 6.11-6.23 (1H, m), 6.67-6.74 (1H, m), 6.81-6.82 (1H, m),6.98-7.09 (1H, m).

[0205] [Manufacturing Example 9]

[0206] Synthesis of 2-nonadecanyl-1-octadecylimidazole

[0207] Under a hydrogen atmosphere, a mixture of 2-(nonadecano-1-enyl)-1-octadecylimidazole (E / Z mixture; 1.5 g, 2.6 mmol), 10% Pd / C (50% aqueous content; 0.30 g), and tetrahydrofuran (100 mL) obtained in Preparation Example 8 was stirred at room temperature and atmospheric pressure for 15 hours. After filtering the mixture, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate = 95 / 5) to obtain 2-nonadecano-1-octadecylimidazole (1.0 g, 67%).

[0208] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.75 (66H, m), 2.60-2.64 (2H, m), 3.79-3.82 (2H, m), 6.79 (1H, d), 6.93 (1H, d).

[0209] [Manufacturing Example 10]

[0210] Synthesis of 2-nonadecanyl-1-octadecylimidazolium hydrochloride

[0211] A 1M solution of hydrogen chloride-diethyl ether (10 mL) was added to a suspension of 2-nonadecanyl-1-octadecylimidazole (0.88 g, 1.5 mmol) and n-hexane (100 mL) obtained in Preparation Example 9 at room temperature, and the mixture was stirred for 1 hour. The solvent in the resulting suspension was removed by vacuum distillation to obtain 2-nonadecanyl-1-octadecylimidazole hydrochloride (0.98 g, 100%).

[0212] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.40 (62H, m), 1.80-1.88 (4H, m), 3.02-3.07 (2H, t), 3.96-4.00 (2H, t), 6.97 (1H, d), 7.29 (1H, d).

[0213] [Example 3]

[0214] Synthesis of 2-nonadecanyl-1-octadecylimidazolium tetra(pentafluorophenyl)borate

[0215] The 2-nonadecanyl-1-octadecylimidazolium hydrochloride (0.98 g, 1.57 mmol) and the lithium tetra(pentafluorophenyl)borate-diethyl ether complex (1.19 g, 1.57 mmol) obtained in Preparation Example 10 were suspended in cyclohexane (30 mL) and then stirred at room temperature for 1 hour. The organic phase was washed with brine, dried using anhydrous magnesium sulfate, and concentrated under reduced pressure. Drying under reduced pressure at 45 °C yielded 2-nonadecanyl-1-octadecylimidazolium tetra(pentafluorophenyl)borate (0.82 g, 94%).

[0216] 1 H NMR (CDCl3) δ: 0.88 (6H, t), 1.25-1.43 (62H, m), 1.66-1.82 (4H, m), 2.81 (2H, t), 3.94 (2H, t), 6.99 (1H, d), 7.03 (1H, d);

[0217] 19 F NMR (CDCl3) δ: -133.9 (8F, t), -164.1 (4F, t), -167.9 (8F, t).

[0218] It can be confirmed that the compound obtained in Example 3 is dissolved in methylcyclohexane at a concentration of 10% by weight.

[0219] [Experimental Example] (Polymerization Performance Evaluation)

[0220] The following illustrates a general polymerization method in which the compounds or compositions of the present invention are used as co-catalysts.

[0221] Inside a glove box, 1-octene, triisobutylaluminum (TIBA, 0.55M n-hexane solution), and solvent (methylcyclohexane (MCH)) were added to a 100 mL autoclave to prepare a comonomer solution. A polymerization catalyst (dimethylsilane-based (tert-butylamide)-(tetramethylcyclopentadienyl)-titanium(IV)-dichloride (CGC)), triisobutylaluminum (0.55M n-hexane solution), and solvent were added to prepare a catalyst solution of a predetermined concentration, which was then transferred to a Schlenk flask. A cocatalyst solution of a predetermined concentration was prepared by dissolving the comonomer solution, catalyst solution, and cocatalyst solution in the solvent, and transferred to a Schlenk flask. Preparation was carried out in a manner that ensured a constant total amount of solvent and triisobutylaluminum during the reaction after mixing the comonomer solution, catalyst solution, and cocatalyst solution. After purging the autoclave with ethylene gas, the catalyst solution and cocatalyst solution were added sequentially to the autoclave. The ethylene pressure was immediately adjusted to a predetermined pressure, and the mixture was stirred at a predetermined temperature (25°C) for a predetermined time. After cooling the reaction mixture to remove ethylene gas, the mixture was then injected into 100 mL of methanol containing 3 mL of hydrochloric acid and stirred at room temperature for 30 minutes. The precipitate was filtered off and dried under reduced pressure at 60 °C to obtain the ethylene-octene copolymer.

[0222] (Melting point determination)

[0223] The melting point was determined using a DSC6220 instrument (Seiko Instruments Inc.) based on differential scanning calorimetry (DSC). The sample (polymer) was heated from 40°C to 150°C at a rate of 10°C / min.

[0224] The results of polymerization reactions using various co-catalysts at 25°C are shown in Table 1 below. As a co-catalyst for Comparative Example 1, N,N-bis(octadecyl)methylammonium tetra(pentafluorophenyl)borate obtained by methods known to the public (e.g., referring to the specification of U.S. Patent No. 6,121,185).

[0225] [Table 1]

[0226]

[0227] Reaction conditions: Catalyst: CGC; Catalyst: Co-catalyst = 1:1; TIBA (total amount 3000 μmol); Solvent: Methylcyclohexane; Total solvent amount (40 mL); 1-Octene (1 mL); Ethylene pressure (8 atm); 25℃.

[0228] 1） Di(octadecyl)methylammonium tetra(pentafluorophenyl)borate

[0229] Table 1 confirms that Examples 1 and 2 both showed higher polymerization activity than Comparative Example 1.

[0230] Industrial availability

[0231] The compounds of the present invention are soluble in hydrocarbon solvents and do not become catalyst poisons; therefore, they are useful as co-catalysts for the polymerization of olefins and dienes.

[0232] This application is based on Japanese Special Application No. 2020-209071 filed in Japan on December 17, 2020, and its contents are fully included in this specification.

Claims

1. A compound represented by the following formula (1), In equation (1), R 1 R 2 R 3 and R 4 All are pentafluorophenyl. [A ＋ [-H] represents a cation obtained by protonation of the cyclic nitrogen atom of 2-nonadecanyl-4-octadecyloxypyridine or 2-nonadecanyl-6-octadecyloxypyridine.

2. A co-catalyst for the polymerization of a monomer, wherein, The polymerization cocatalyst comprises the compound of claim 1, wherein the monomer is at least one monomer selected from the group consisting of olefins and dienes.

3. A method for manufacturing a polymer, comprising: Using the compound of claim 1 as a co-catalyst, at least one monomer selected from the group consisting of olefins and dienes is polymerized.

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