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  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
  • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds

Definitions

• the present invention relates to a composition containing a borate compound and a base, which is useful as an auxiliary catalyst for the polymerization of olefins and diene, and a method for producing the same.
• non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes are used as catalysts for polymerization of olefins and dienes.
• metallocene compounds such as metallocene compounds, diimine complexes, and phenoxy complexes
• phenoxy complexes are used as catalysts for polymerization of olefins and dienes.
• methylaluminoxane and tetrakis (pentafluorophenyl) borate compounds are used as cocatalysts for stabilizing active species.
• Tetrakis (pentafluorophenyl) borate compounds have better thermal stability than methylaluminoxane, and the stoichiometric ratio used for metal complexes is smaller than that of methylaluminoxane, so they are co-catalysts in solution polymerization systems. Widely used as.
• a non-polar hydrocarbon solvent is used as the solvent used in the polymerization of olefins and dienes using a metal complex catalyst.
• a metal complex catalyst for preventing odor and toxicity, switching from aromatic hydrocarbon solvents such as toluene to aliphatic hydrocarbon solvents such as hexane is progressing.
• tetrakis (pentafluorophenyl) borate compounds are sparingly soluble in aliphatic hydrocarbon solvents such as hexane and heptane
• tetrakis (pentafluorophenyl) borate compounds that are soluble in aliphatic hydrocarbon solvents Is desired and proposed (Patent Document 2).
• Di (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate and bis (hydrogenated beef tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate described in Patent Document 2 are useful as compounds easily soluble in hydrocarbon solvents. ..
• Patent Document 2 the production method described in Patent Document 2 is prepared by reacting lithium tetrakis (pentafluorophenyl) borate with a separately prepared dialkylmethylamine hydrochloride, and this method is sparingly soluble in water.
• the raw material lithium tetrakis (pentafluorophenyl) borate or long-chain aliphatic amine hydrochloride remains in the product, which becomes a catalytic poison and does not show sufficient activity when used as a co-catalyst for polymerization. I was concerned.
• Patent Document 3 discloses a method for producing an ammonium tetrakis (pentafluorophenyl) borate derivative, which is obtained by mixing an alkali metal salt of tetrakis (pentafluorophenyl) borate and an amine and then treating with a protonic acid.
• an ether complex of an alkali metal salt of tetrakis (pentafluorophenyl) borate or a protonate of a long-chain aliphatic amine would remain in the product and act as a catalytic poison.
• Patent Document 4 discloses a composition containing a trialkylammonium tetrakis (pentafluorophenyl) borate compound and an amine compound, and a method for producing the same, and discloses that the composition is soluble in a hydrocarbon solvent. There is. However, since trialkylamine, which is an amine compound described in Patent Document 4, has high basicity and nucleophilicity, there is a concern that it may be a catalytic poison for the polymerization reaction of olefins and dienes.
• JP-A-2018-104335 Special Table 2000-507157 Japanese Patent Application Laid-Open No. 2007-530673 JP-A-2019-59795
• the present invention provides a borate compound-containing composition and an industrial production method thereof, which is soluble in a hydrocarbon solvent, particularly an aliphatic hydrocarbon solvent, and does not act as a catalytic poison for the polymerization reaction of olefins and dienes. To provide.
• R and R' are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6 Represents a -14 aryl group.
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• [AH] + represents a cation derived from base A.
• the base A is (I) A nitrogen-containing aromatic heterocyclic compound having 25 or more total carbon atoms substituted with the same or different two or more C 1-30 alkyl groups or C 1-30 alkoxy groups, or (ii) the following formula (ii) 2):
• the composition containing the compound represented by (hereinafter, also referred to as "the composition of the present invention") is soluble in a hydrocarbon solvent, particularly an aliphatic hydrocarbon solvent, and is responsible for the polymerization reaction of olefins and dienes. For the first time, we have found that it is useful as a co-catalyst without generating a compound that becomes a catalytic poison, and have completed the present invention.
• R and R' are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6 Represents a -14 aryl group.
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• [AH] + represents a cation derived from base A.
• the base A is (I) A nitrogen-containing aromatic heterocyclic compound having 25 or more total carbon atoms substituted with the same or different two or more C 1-30 alkyl groups or C 1-30 alkoxy groups, or (ii) the following formula (ii) 2):
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• [AH] + represents a cation derived from base A.
• the base A is (I) A nitrogen-containing aromatic heterocyclic compound having 25 or more total carbon atoms substituted with the same or different two or more C 1-30 alkyl groups or C 1-30 alkoxy groups, or (ii) the following formula (ii) 2):
• Ar represents a optionally substituted C 6-14 aryl group, and R 5 and R 6 each independently represent an optionally substituted C 1-30 alkyl group.
• a composition containing a compound represented by. [2'] The composition according to the above [1], wherein the component (I) is a base A.
• R 1 , R 2 , R 3 and R 4 are all pentafluorophenyl groups, 2, 2', 3, 3', 4', 5, 5', 6, 6'-nonafluoro-4- ( 1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7,8-heptafluoro-2-
• [6] A 5- or 6-membered monocyclic nitrogen-containing aromatic having 35 or more total carbon atoms in which the base A is substituted with two identical or different C 9-30 alkyl groups or C 9-30 alkoxy groups.
• the base A is an aromatic amine compound having a total carbon number of 25 or more represented by the above formula (2).
• Ar is a phenyl group optionally substituted with a substituent selected from the group consisting of a halogen atom, a C 1-30 alkyl group, a C 1-30 alkoxy group and a halo C 1-6 alkyl group, and R.
• the contents of the base A per 1 mol of the compound represented by the formula (1) are in the range of 0.01 to 10 mol, and the above [1], [2], [2'] and [4]. ]
• R and R' are independently C 1-30 alkyl groups, and the total carbon number of R and R'is 8 or more, as described above [1] and [3] to [5]. ]
• R 1 , R 2 , R 3 and R 4 each independently represent a C 6-14 aryl group substituted with one or more fluorine atoms or fluoro C 1-4 alkyl groups.
• the present invention comprises a step of reacting the compound represented by the above with the base A, and the amount of the base A exceeding 1 mol is used with respect to 1 mol of the compound represented by the formula (3).
• [17] The production method according to [16], wherein the amount of the base A used per 1 mol of the compound represented by the formula (3) is in the range of 1.01 to 3 mol.
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• M represents an alkali metal or an alkaline earth metal, and n represents 1 or 2.
• the step of reacting the compound represented by the above formula (4) with the base A and the protonic acid is included, and an amount of more than 1 mol of the base A is used with respect to 1 mol of the compound represented by the formula (4).
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• M represents an alkali metal or an alkaline earth metal, and n represents 1 or 2.
• R and R' are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6 Represents a -14 aryl group.
• a polymer comprising polymerizing at least one monomer selected from the group consisting of olefins and dienes using the composition according to any one of [1] to [14] above as a co-catalyst. Manufacturing method.
• a composition containing the above-mentioned borate compound, which is soluble in a hydrocarbon solvent, particularly an aliphatic hydrocarbon solvent, and useful as an auxiliary catalyst for the polymerization reaction of olefins and diene, and a method for producing the same can be provided.
• halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• alkyl (group) means a linear or branched-chain alkyl group having 1 or more carbon atoms.
• C 1-30 alkyl (group) means an alkyl group having 1 to 30 carbon atoms in a straight chain or a branched chain, and for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like.
• C 9-30 alkyl (group) means an alkyl group having 9 to 30 carbon atoms in a straight chain or a branched chain, and for example, nonyl, decyl, undecyl, dodecyl, tridecylic, tetradecyl, and the like.
• Hexadecyl, octadecyl, nonadecylic, eikosyl, docosyl, tricosylic, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonadecylic, triacoylic acid and the like can be mentioned.
• C 1-6 alkyl (group) means an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, and for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like.
• Examples include sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like. Be done. Of these, the C 1-4 alkyl group is preferable.
• halo C 1-6 alkyl (group) means a group in which one or more hydrogen atoms in the "C 1-6 alkyl” group are substituted with halogen. Specifically, for example, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoro.
• the "fluoro C 1-6 alkyl (group)” means a group in which the halogen atom in the "halo C 1-6 alkyl” group is a fluorine atom.
• Examples thereof include propyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl and the like.
• difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 3 , 3,3-Trifluoropropyl, 4,4,4-trifluorobutyl and other " fluoroC 1-4 alkyl (groups)" are preferred, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl , Pentafluoroethyl or pentafluoroethyl is more preferred, and trifluoromethyl is particularly preferred.
• cycloalkyl (group) means a cyclic alkyl group, and is preferably a C 3-8 cycloalkyl group unless the carbon number range is particularly limited.
• C 3-8 cycloalkyl (group) means a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Can be mentioned. Of these, the C 3-6 cycloalkyl group is preferable.
• alkoxy (group) means a group in which a linear or branched alkyl group is bonded to an oxygen atom.
• C 1-30 alkoxy (group) means an alkoxy group having 1 to 30 carbon atoms in a linear or branched chain, and for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy.
• C 9-30 alkoxy (group) means an alkoxy group having 9 to 30 carbon atoms in a straight chain or a branched chain, and for example, nonyloxy, decyloxy, undecyloxy, dodecyloxy, or tri. Decyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, nonadesyloxy, eikosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy , Nonacosyloxy, triacoxyloxy and the like.
• C 1-6 alkoxy (group) means an alkoxy group having 1 to 6 carbon atoms in a linear or branched chain, and for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy. , Se-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like. Of these, the C 1-4 alkoxy group is preferable.
• halo C 1-6 alkoxy (group) means a group in which one or more hydrogen atoms in the "C 1-6 alkoxy” group are substituted with halogen atoms.
• the "fluoro C 1-6 alkoxy (group)” means a group in which the halogen atom in the "halo C 1-6 alkoxy” group is a fluorine atom.
• Examples thereof include propoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, 5,5,5-trifluoropentyloxy, 6,6,6-trifluorohexyloxy and the like.
• difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 3 , 3,3-Trifluoropropoxy, 4,4,4-trifluorobutoxy and the like " fluoroC 1-4 alkoxy (group)" are preferable, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy.
• Pentafluoroethoxy or pentafluoroethoxy is more preferred, and trifluoromethoxy is particularly preferred.
• aryl (group) means a monocyclic or polycyclic (condensed) hydrocarbon group exhibiting aromaticity, and specifically, for example, phenyl, 1-naphthyl, and the like. Examples thereof include C 6-14 aryl groups such as 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthril, 3-phenanthryl and 9-phenanthryl. Of these, phenyl, 1-naphthyl or 2-naphthyl is preferred.
• the "nitrogen-containing aromatic heterocyclic compound” is a monocyclic compound containing 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom as a ring-constituting atom. It is a fused polycyclic aromatic heterocyclic compound and means a compound containing at least one nitrogen atom as a ring-constituting atom.
• nitrogen-containing aromatic heterocyclic compound examples include, for example, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isooxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxa.
• 5- or 6-membered monocyclic nitrogen-containing aromatic heterocycles such as diazole, 1,3,4-oxadiazole, 1,2,4-thiazazole, 1,3,4-thiazazole, triazole, tetrazole, triazine, etc.
• a 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound or a bicyclic nitrogen-containing aromatic heterocyclic compound is preferable.
• the 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound pyridine or imidazole is more preferable, and as the bicyclic nitrogen-containing aromatic heterocyclic compound, benzimidazole is more preferable. Of these, pyridine or imidazole is particularly preferable.
• a halogen atom, a cyano group, a C 1-6 alkyl group, a halo C 1-6 alkyl group, a C 1-6 alkoxy group, a halo C 1-6 alkoxy group or a phenyl group are preferable, and a halogen atom (eg, a fluorine atom) is preferable.
• C 1-6 alkyl group eg, methyl, ethyl
• C 1-6 alkoxy group eg, methoxy, ethoxy
• halo C 1-6 alkyl group eg, trifluoromethyl
• each substituent may be the same or different.
• the substituent may be further substituted with one or more C 1-6 alkyl groups, C 1-6 alkoxy groups, halogen atoms, phenyl groups and the like.
• hydrocarbon solvent means a solvent including an aromatic hydrocarbon solvent and / or an aliphatic hydrocarbon solvent. Of these, an aliphatic hydrocarbon solvent is preferable from the viewpoint of odor and toxicity.
• aromatic hydrocarbon solvent examples include benzene, toluene, xylene and the like.
• examples of the "aliphatic hydrocarbon solvent” include n-hexane, isohexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and mixed solvents thereof.
• soluble in a hydrocarbon solvent means a solution of a hydrocarbon solvent (or an aliphatic hydrocarbon solvent) and the composition of the present invention at 25 ° C. It means that the composition of the present invention dissolves at a concentration of 5% by weight or more to form a transparent uniform solution.
• soluble in a hydrocarbon solvent or an aliphatic hydrocarbon solvent
• composition of the present invention Hereinafter, the composition of the present invention will be described.
• composition of the present invention (I) Base A or the following formula (5):
• R and R' are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6 Represents a -14 aryl group.
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• [AH] + represents a cation derived from base A.
• the base A is (I) A nitrogen-containing aromatic heterocyclic compound having 25 or more total carbon atoms substituted with the same or different two or more C 1-30 alkyl groups or C 1-30 alkoxy groups, or (ii) the following formula (ii) 2):
• Ar represents a optionally substituted C 6-14 aryl group
• R 5 and R 6 each independently represent an optionally substituted C 1-30 alkyl group.
• the nitrogen-containing aromatic heterocyclic compound of base A is a 5- or 6-membered monocyclic compound substituted with two identical or different C 9-30 alkyl groups or C 9-30 alkoxy groups.
• Nitrogen-containing aromatic heterocyclic compounds eg, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isooxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazol, 1,3,4- Oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetrazole, triazine, etc.
• Pyridine or imidazole substituted with is more preferred.
• the nitrogen-containing aromatic heterocyclic compound preferably has a total carbon number of 25 or more
• nitrogen-containing aromatic heterocyclic compound as base A examples include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecil-5-octadecylpyridine, 2-nonadecil.
• Examples thereof include -4-octadecyloxypyridine, 2-nonadecil-6-octadecyloxypyridine, 4-nonadecil-1-octadecil imidazole, 5-nonadecil-1-octadecil imidazole, 2-nonadecil-1-octadecil imidazole and the like.
• Aromatic heterocyclic compounds eg, benzoimidazole, benzoxazole, benzoisoxazole, benzothiazole, benzoisothiazole, benzotriazole, imidazolepyridine, thienopyridine, flopyridine, pyrrolopyridine, pyrazolopyridine, oxazolopyridine, thiazolopyridine, Imidazopyrimidine, imidazopyrimidine, thienopyrimidine, flopyrimidine, pyrrolopyrimidine, pyrazolopyrimidine, oxazolopyrimidine, thiazolopyrimidine, pyrazolotriadin, indole, isoindole, 1H-indazole, purine, isoquinoline, quinoline, phthalazine
• nitrogen-containing aromatic heterocyclic compound as base A examples include, for example, 2,6-dinonadecylbenzoimidazole, 1,2-dioctadecylbenzoimidazole, 1,2-diheptadecylbenzimidazole. , 2-Heptadecyl-1-octadecylbenzimidazole, 1-heptadecyl-2-octadecylbenzimidazole and the like.
• Ar in the formula (2) is preferably composed of a halogen atom, a cyano group, a C 1-30 alkyl group, a halo C 1-6 alkyl group, a C 1-30 alkoxy group, and a halo C 1-6 alkoxy group. It is a C 6-14 aryl group which may be substituted with a substituent selected from the group, more preferably a halogen atom, a C 1-30 alkyl group, a C 1-30 alkoxy group and a halo C 1-6.
• phenyl group a 1-naphthyl group or a 2-naphthyl group (particularly preferably a phenyl group) which may be substituted with a substituent selected from the group consisting of alkyl groups.
• Ar even if it is substituted with a substituent selected from the group consisting of a halogen atom, a C 1-6 alkyl group, a C 1-6 alkoxy group and a halo C 1-6 alkyl group. It is a good phenyl group.
• the total carbon number of the compound (2) is preferably 30 or more, and more preferably 35 or more.
• R 5 and R 6 in the formula (2) are preferably C 1-30 alkyl groups which may be independently substituted with a halogen atom (eg, a fluorine atom), and more preferably.
• a halogen atom eg, a fluorine atom
• Each independently is a C 1-30 alkyl group, more preferably a C 9-30 alkyl group, and particularly preferably the same C 14-30 alkyl group.
• Suitable compounds (2) include the following compounds.
• Ar in the formula (2) consists of a halogen atom, a cyano group, a C 1-30 alkyl group, a halo C 1-6 alkyl group, a C 1-30 alkoxy group, and a halo C 1-6 alkoxy group.
• R 5 and R 6 are C 1-30 alkyl groups that may be independently substituted with halogen atoms (eg, fluorine atoms), and have a total carbon number of 25 or more (preferably 30 or more).
• halogen atoms eg, fluorine atoms
• Ar in the formula (2) may be substituted with a substituent selected from the group consisting of a halogen atom, a C 1-30 alkyl group, a C 1-30 alkoxy group and a halo C 1-6 alkyl group. , Phenyl group, 1-naphthyl group or 2-naphthyl group (preferably phenyl group).
• R 5 and R 6 are independently C 1-30 alkyl groups and have a total carbon number of 35 or more.
• Ar in the formula (2) is a phenyl group.
• Preferred specific examples of compound (2) include, for example, N, N-dihexadecylaniline, N, N-dioctadecylaniline, N, N-didocosylaniline and the like.
• the base A a commercially available product may be used as it is, or a compound obtained by the production method shown below may be used.
• Compound (2) has the following formula:
• X represents a halogen atom, and the definitions of other symbols are synonymous with the above.
• a base in a solvent inert to the reaction, be prepared by sequentially reacting an aniline derivative (a1) with an alkyl halide (R 5 -X and R 6 -X) can.
• compound (2) can be produced from the aniline derivative (a1) in one step.
• the amount of the alkyl halide (R 5 -X or R 6 -X) is aniline derivative ((a1) or (a2)) relative to 1 mol, 1 to 2 mol (preferably 1 to 1.2 moles ).
• the amount of the alkyl halide used is 2 to 4 mol (preferably 2 to 3 mol) with respect to 1 mol of the aniline derivative (a1).
• the reaction solvent is not particularly limited, but for example, ether solvents such as tetrahydrofuran and diethoxyethane, toluene, dimethylformamide, dimethyl sulfoxide and the like are preferable.
• Examples of the base include sodium hydride, potassium carbonate, tert-potassium butoxy and the like.
• the amount of the base used is 1 to 2 mol (preferably 1 to 1.2 mol) with respect to 1 mol of the aniline derivative ((a1) or (a2)).
• the reaction temperature is preferably room temperature to 180 ° C.
• the reaction time is usually 1 to 48 hours.
• the nitrogen-containing aromatic heterocyclic compound having 25 or more total carbon atoms has the following formula:
• the group represented by is a nitrogen-containing aromatic heterocyclic group, X'represents a halogen atom, R 7 is a optionally substituted C 1-30 alkyl group, and n1 is 2 or more. Represents an integer of. ),
• the compound (a4) is obtained by reacting the compound (a3) with a phosphonium salt (R 7- CH 2 PPh 3 X') in the presence of a base in a solvent that does not affect the reaction.
• the base (A2) can be produced by the reaction with the reducing agent (step 1) (step 1).
• Examples of the base used in the step 1 include sodium hydride, potassium carbonate, tert-butoxypotassium and the like.
• the amount of the base used is 1 to 2 mol (preferably 1 to 1.2 mol) with respect to the equivalent amount (1 mol) of the formyl group of the compound (a3).
• the amount of the phosphonium salt (R 7- CH 2 PPh 3 X') used is also 1 to 2 mol (preferably 1 to 1 mol) with respect to the equivalent (1 mol) of the formyl group of compound (a3). 2 mol).
• the reaction solvent in step 1 is not particularly limited, but for example, an ether solvent such as tetrahydrofuran and diethoxyethane, an aromatic hydrocarbon solvent such as toluene, an aliphatic hydrocarbon solvent such as hexane, dimethylformamide, dimethyl sulfoxide and the like. Is preferable.
• the reaction temperature in step 1 is preferably room temperature to 180 ° C.
• the reaction time of step 1 is usually 0.5 to 48 hours.
• step 2 hydrogen, ammonium formate, ammonium chloride and the like can be used as the reducing agent in the presence of a metal catalyst.
• a metal catalyst a transition metal catalyst such as Pd / C or Pt / C is preferable.
• the amount of the metal catalyst used is 0.001 to 1.0 mol (preferably 0.01 to 0.5 mol) with respect to 1 mol of the double bond of the compound (a4).
• the reaction solvent in step 2 is not particularly limited, but for example, hexane, toluene, tetrahydrofuran, ethanol and the like are preferable, and a mixed solvent thereof may be used.
• conditions such as normal pressure and medium pressure can be appropriately selected according to the progress of the reaction.
• the reaction temperature in step 2 is preferably room temperature to 180 ° C.
• the reaction time of step 2 is usually from 1 hour to 72 hours.
• the total carbon number of R and R' is 8 or more, preferably 16 or more.
• the total carbon number of R and R' may be 20 or more, 25 or more, or 28 or more.
• the total carbon number of R and R' is preferably 32 or less.
• R and R' are independent, optionally substituted C 1-30 alkyl group, optionally substituted C 3-15 cycloalkyl group or optionally substituted C 6-14 aryl group, respectively.
• C 1-30 alkyl groups (preferably C 1-18 alkyl groups such as methyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.), particularly preferably independently of C. It is a 14-30 alkyl group.
• Examples of the suitable compound (5) include the following compounds.
• R and R'in the formula (5) are independently C 1-30 alkyl groups, and the total carbon number of R and R'is 8 or more. Compound (5).
• R and R'in the formula (5) are independently C 1-30 alkyl groups, and the total carbon number of R and R'is 10 or more. Compound (5).
• R and R'in the formula (5) are independent of each other.
• Halogen atom A C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) C 1-30 alkoxy group and (3) halo C 1-30 alkoxy group;
• R and R'in the formula (5) are independently C 1-30 alkyl groups or (1) halogen atoms.
• the total number of carbon atoms is 16 or more, Compound (5).
• R and R'in the formula (5) are independent of each other.
• the number is 16 or more, Compound (5).
• R and R'in the formula (5) are independently C 1-30 alkyl groups, and the total carbon number of R and R'is 16 or more. Compound (5).
• Preferred specific examples of the compound (5) include, for example, dibutyl ether, dihexyl ether, dioctyl ether, didecyl ether, didodecyl ether, ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, docosyl ethyl ether, tetra. Examples thereof include decyloxyethyl tetradecyl ether, cyclopentyl methyl ether, diphenyl ether, octadecyl phenyl ether, etc.
• R and R'of ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, dinonadecyl ether and the like are independently C 14-30 alkyl groups and of R and R', respectively.
• the compound (5) having a total carbon number of 16 or more and 32 or less is more preferable.
• the compound (5) having a total carbon number of 7 or less in R and R' has a low boiling point, there is a concern that it is industrially difficult to control its content, and it can be a catalytic poison. Not preferable.
• R 1 , R 2 , R 3 and R 4 are preferably phenyls, each independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl groups).
• R 2, R 3 and R 4 are all the same, pentafluorophenyl group, 2,2 ', 3,3', 4 ', 5,5', 6,6'-nonafluoro-4- (1, 1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group Is.
• a preferred embodiment of A in [AH] + which is a cation derived from base A, is the same as described above.
• Suitable compounds (1) include the following compounds.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl group).
• R 5 and R 6 are C 1-30 alkyl groups that may be independently substituted with halogen atoms (eg, fluorine atoms), and have a total carbon number of 25 or more (preferably 30 or more). ), Compound (1).
• R 1 , R 2 , R 3 and R 4 in the formula (1) are independently substituted with one or more fluorine atoms or trifluoromethyl groups, such as a phenyl group, a 1-naphthyl group or a group.
• 2-naphthyl group, A is represented by the above formula (2)
• Ar in the formula (2) is selected from the group consisting of a halogen atom, a C 1-30 alkyl group, a C 1-30 alkoxy group and a halo C 1-6 alkyl group.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are all the same pentafluorophenyl groups 2, 2', 3, 3', 4', 5, 5', 6, 6 '-Nonafluoro-4- (1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7, 8-Heptafluoro-2-naphthyl group, A is represented by the above formula (2), and Ar in the formula (2) is a phenyl group.
• Compound (1), wherein R 5 and R 6 are the same C 14-30 alkyl group and have a total carbon number of 35 or more.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl group).
• R 1 , R 2 , R 3 and R 4 in the formula (1) are independently substituted with one or more fluorine atoms or trifluoromethyl groups, such as a phenyl group, a 1-naphthyl group or a group.
• Decylpyridine 2-Nonadecyl-5-Octadecylpyridine, 2-Nonadecyl-4-octadecyloxypyridine, 2-Nonadecyl-6-Octadecyloxypyridine, 4-Nonadecyl-1-octadecylimidazole, 5-Nonadecyl-1-octadecilimidazole, Alternatively, compound (1) which is 2-nonadecil-1-octadecylimidazole) and has a total carbon number of 35 or more.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are all the same pentafluorophenyl group 2, 2', 3, 3', 4', 5, 5', 6, 6 '-Nonafluoro-4- (1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7, 8-Heptafluoro-2-naphthyl group (preferably pentafluorophenyl group), Pyridine in which A is substituted with two identical or different C 14-30 alkyl groups or C 14-30 alkoxy groups (preferably 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-Nonadecyl-5-octadecylpyridine, 2-nonadecil-4-octadecyloxypyridine or 2-nonadecil-6-octa
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl group).
• a bicyclic nitrogen-containing aromatic heterocyclic compound in which A is substituted with the same or different two or more C 9-30 alkyl groups or C 9-30 alkoxy groups eg, benzoimidazole, benzoxazole, benzoiso).
• R 1 , R 2 , R 3 and R 4 in the formula (1) are independently substituted with one or more fluorine atoms or trifluoromethyl groups, such as a phenyl group, a 1-naphthyl group or a group.
• 2-naphthyl group Benzimidazole in which A is substituted with two identical or different C 14-30 alkyl groups or C 14-30 alkoxy groups (preferably 2,6-dinonadecylbenzoimidazole, 1,2-dioctadecylbenzo).
• Compound (1) which is imidazole, 1,2-diheptadecylbenzimidazole, 2-heptadecyl-1-octadecilbenzoimidazole or 1-heptadecyl-2-octadecilbenzimidazole) and has a total carbon number of 35 or more. ..
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are all the same pentafluorophenyl group 2, 2', 3, 3', 4', 5, 5', 6, 6 '-Nonafluoro-4- (1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7, 8-Heptafluoro-2-naphthyl group (preferably pentafluorophenyl group), Benzimidazole in which A is substituted with two identical or different C 14-30 alkyl groups or C 14-30 alkoxy groups (preferably 2,6-dinonadecylbenzoimidazole, 1,2-dioctadecylbenzo).
• Compound (1) which is imidazole, 1,2-diheptadecylbenzimidazole, 2-heptadecyl-1-octadecilbenzoimidazole or 1-heptadecyl-2-octadecilbenzimidazole) and has a total carbon number of 35 or more. ..
• Preferred specific examples of the compound (1) include, for example, N, N-dioctadecylanilinium tetrakis (pentafluorophenyl) borate, 2,6-dinonadecylpyridinium tetrakis (pentafluorophenyl) borate, 2-nonadecil-5.
• the compound (1) for example, 2,6-dinonadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate, 1,2-dioctadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate, 1,2-Diheptadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate, 2-heptadecyl-1-octadecilbenzoimidazolium tetrakis (pentafluorophenyl) borate, 1-heptadecyl-2-octadecylbenzoimidazolium tetrakis (pentafluoro) Phenyl) borate, 2-heptadecyl-1-octadecilbenzoimidazolium tetrakis (pentafluorophen
• the base A and the A constituting [AH] + in the compound (1) are preferably the same.
• a preferable embodiment of [AH] + includes a cation in which a proton is added to each of the preferred embodiments of the base A.
• the content of base A is usually 0.01 to 10 mol, preferably 0.01 to 2 mol, more preferably 0, with respect to 1 mol of compound (1). It is 0.01 to 1 mol, particularly preferably 0.01 to 0.5 mol.
• the compounding amount ratio of the compound (5) and the compound (1) is not particularly limited, but the content of the compound (5) is determined from the viewpoint of improving the solubility in the aliphatic hydrocarbon solvent.
• Compound (1) 0.1 mol or more, preferably 0.1 to 10 mol, and more preferably 0.1 to 3 mol, relative to 1 mol.
• the composition of the present invention is soluble in a hydrocarbon solvent at room temperature (15-30 ° C). Further, the conventionally known borate-type co-catalyst is insoluble in an aliphatic hydrocarbon solvent such as n-hexane, whereas the composition of the present invention has good solubility in an aliphatic hydrocarbon solvent. As shown, it is useful as an auxiliary catalyst for the polymerization reaction of homogeneous olefins and dienes.
• Method for producing the composition of the present invention a method for producing the composition of the present invention (hereinafter, also referred to as “the method for producing the present invention”) will be described.
• the composition of the present invention can be a catalytic poison by forming a complex with an ether compound having a total carbon number of 7 or less, and is a hydrogenated borate compound represented by the formula (3) described later (for example, hydrogenated tetrakis (penta)). It is preferable that it does not contain (fluorophenyl) borate) or a metal salt of a tetra-substituted borate compound described later (for example, lithium tetrakis (pentafluorophenyl) borate). Further, the composition of the present invention preferably does not contain an ether compound having a total carbon number of 7 or less, which can be a catalytic poison. The fact that an ether compound having a total carbon number of 7 or less is not contained means that an ether compound having a total carbon number of 7 or less is not detected as a result of 1 H-NMR analysis.
• the manufacturing method of the present invention (hereinafter, also referred to as “manufacturing method 1 of the present invention") is described by the following formula (3) :.
• Examples of the compound (3) used as a raw material in the above production method include hydrogenated tetrakis (pentafluorophenyl) borate, hydrogenated tetrakis (nonafluoro [1,1'-biphenyl] -4-yl) borate, and hydrogenation.
• Known compounds such as tetrakis (heptafluoro-2-naphthyl) borate and hydrogenated [3,5-bis (trifluoromethyl) phenyl] bolate can be mentioned.
• the method for producing the compound (3) is not particularly limited, but for example, the formula (4):
• R 1 , R 2 , R 3 and R 4 each independently represent one or more C 6-14 aryl groups substituted with a fluorine atom or a fluoro C 1-4 alkyl group.
• M represents an alkali metal such as lithium, potassium and sodium, or an alkaline earth metal such as calcium, magnesium and barium, and n represents 1 or 2.
• compound (4) a method of treating with a protonic acid and the like can be mentioned.
• the compound (4) used for producing the compound (3) a commercially available product or a refined product may be used, or a method known per se (for example, Angew. Chem. Int. Ed., 2009, 48 (40)). ), 7444-7447).
• the solvent used in the production of the compound (3) is not particularly limited, but is an ether solvent such as diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether and diisopropyl ether, a halogen solvent such as dichloromethane and chloroform, and the like. It is desirable to use an aromatic hydrocarbon solvent such as toluene and benzene, and an aliphatic hydrocarbon solvent such as n-hexane, isohexane, n-heptane, octane, cyclohexane and methylcyclohexane. Moreover, you may use these solvents alone or in mixture.
• the protonic acid used when treating the compound (4) is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, and hydroiodic acid.
• the amount of protonic acid used in the production of compound (3) is preferably 1 mol per 1 mol of compound (4).
• 1 mol or more of the protonic acid it is preferable to wash the organic phase with water until the pH of the aqueous phase after washing with water becomes 3 or more so that the protonic acid used in the treated organic phase does not remain.
• the pH of the aqueous phase is less than 3, the protonate used in the organic phase remains, and in the reaction with base A, the protonate of base A is generated and remains in the composition of the present invention. Therefore, there is a concern that it may become a catalytic poison during polymerization.
• the solution of the compound (3) prepared as described above can be used as it is for the reaction with the base A.
• Examples of the base A used in the production method 1 of the present invention include the above-mentioned compounds having a total carbon number of 25 or more (preferably 30 or more, more preferably 35 or more).
• Specific examples of the base A include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecil-5-octadecylpyridine, 2-nonadecil-4-octadecyloxypyridine, and 2-nonadecil.
• Nitrogen-containing aromatic heterocyclic compounds such as -6-octadecyloxypyridine, 4-nonadecil-1-octadecil imidazole, 5-nonadecil-1-octadecil imidazole, 2-nonadecil-1-octadecil imidazole; N, N-dihexadecyl
• aromatic amine compounds such as aniline, N, N-dioctadecylaniline, N, N-dinonadecylaniline, and N, N-didocosylaniline.
• the compound (3) and the base A having two or more C 9-30 alkyl groups (preferably C 14-30 alkyl groups) or C 9-30 alkoxy groups (preferably C 14-30 alkoxy groups).
• the composition containing the base A and the compound (1) obtained by the reaction with is also soluble in the aliphatic hydrocarbon solvent.
• an amount of base A exceeding 1 mol is used for 1 mol of compound (3). By doing so, it is possible to prevent the unreacted compound (3) from remaining in the composition as a product.
• the amount of base A used per 1 mol of compound (3) is in the range of 1.01 to 5.0 mol, preferably in the range of 1.01 to 2.0 mol, and particularly preferably 1.01. ⁇ 1.5 mol.
• an ether solvent having a total carbon number of 7 or less (that is, an ether compound) or a compound (3) to which water is added remains in the composition as a product.
• an ether compound having a total carbon number of 7 or less or a compound (3) to which water is added acts as a catalyst poison. Further, when the amount of the base A used is 1 mol with respect to the compound (3), the solubility of the composition of the present invention in the aliphatic hydrocarbon solvent is lowered.
• the reaction temperature and time in the production method 1 of the present invention are not particularly limited, but the reaction temperature is usually 10 ° 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.
• the reaction solution is dehydrated with a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and then the solvent is removed to contain the base A and the compound (1).
• a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate
• the preferred embodiment of the compound (3) is based on the preferred embodiment of the anion moiety in the compound (1) (the anion moiety of the compounds (1-1) to (1-9)).
• Suitable compounds (4) include the following compounds.
• R 1 , R 2 , R 3 and R 4 in the above formula (4) are independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl group).
• R 1 , R 2 , R 3 and R 4 in the formula (4) are each independently substituted with one or more fluorine atoms or trifluoromethyl groups, such as a phenyl group, a 1-naphthyl group or a group. 2-naphthyl group, Compound (4), wherein M is lithium, sodium or potassium, and n is 1.
• R 1 , R 2 , R 3 and R 4 in the above formula (4) are all the same pentafluorophenyl groups 2, 2', 3, 3', 4', 5, 5', 6, 6 '-Nonafluoro-4- (1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6,7, 8-Heptafluoro-2-naphthyl group, Compound (4), wherein M is lithium or sodium and n is 1.
• Preferred specific examples of the compound (4) include, for example, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, lithium tetrakis (nonafluoro [1,1'-biphenyl] -4-yl) borate, and the like.
• Another preferred embodiment of the manufacturing method of the present invention includes the following manufacturing methods (manufacturing method 2 and manufacturing method 3 of the present invention).
• composition of the present invention has the following formula:
• the amount of base A, protonic acid and compound (4) used in the production method 2 of the present invention, the reaction solvent, the reaction temperature, the reaction time, etc. are the same as those in the production method 1 of the present invention described above.
• composition of the present invention has the following formula:
• the amount of the compound (5) used in the production method 3 of the present invention is 0.1 mol or more, preferably 0.1 to 10 mol, with respect to 1 mol of the compound (1) (compound (4)). It is in moles, more preferably in the range of 0.1 to 3 moles. When the amount of compound (5) is less than 0.1 mol, the solubility of the composition of the present invention decreases.
• the type, amount, reaction solvent, reaction temperature, reaction time, etc. of the base A, the protonic acid, and the compound (4) used in the production method 3 of the present invention are the same as those in the production method 1 of the present invention.
• composition of the present invention contains base A or compound (5), and compound (1), is soluble (or easily soluble) in a hydrocarbon solvent, particularly an aliphatic hydrocarbon solvent, and is basic and It does not contain compounds that can be catalytic poisons, such as highly nucleophilic amine compounds, base A protonates, and ether compounds with a total carbon number of 7 or less. Therefore, it is useful as an auxiliary catalyst for polymerization of olefins and diene.
• a hydrocarbon solvent particularly an aliphatic hydrocarbon solvent
• the present invention includes a method for producing a polymer, which comprises polymerizing at least one monomer selected from the group consisting of olefins and dienes using the composition of the present invention as a co-catalyst. It is known, for example, described in Patent Document 2 to polymerize at least one monomer selected from the group consisting of olefins and dienes by using a borate compound similar to the compound (1) of the present invention as a co-catalyst. Therefore, except that the composition of the present invention is used as a co-catalyst, the method for producing a polymer of the present invention can be carried out with reference to the method for producing a polymer described in Patent Document 2 described above. ..
• % Indicates mol / mol% for yield, and% by weight for others unless otherwise specified. Further, the room temperature means a temperature of 15 ° C. to 30 ° C. unless otherwise specified.
• Example 1 Composition containing N, N-dioctadecylanilineium tetrakis (pentafluorophenyl) borate and N, N-dioctadecylaniline N, N-dioctadecylaniline (4.3 g, 7.2 mmol) and lithium tetrakis (pentafluoro)
• a tridiethyl ether complex of phenyl) borate manufactured by AGC Wakasa Chemical Co., Ltd.
• 5.0 g, 5.5 mmol was suspended in n-hexane (50 mL), and then a 1.0 M hydrogen chloride-diethyl ether solution (5).
• Example 1 It was confirmed that the composition obtained in Example 1 was soluble in n-hexane and cyclohexane at a concentration of 20% by weight.
• Example 2 Composition containing N, N-dioctadecylanilinium tetrakis (pentafluorophenyl) borate and N, N-dioctadecylaniline N, N-dioctadecylanilinium tetrakis (pentafluorophenyl) borate (128 mg, 0.1 mmol) N-Hexane (512 mg) was added to the mixture, and the mixture was stirred (concentration: 20% by weight).
• N, N-dioctadecylaniline 24 mg, 0.04 mmol was added to the obtained bilayer separation solution, and the mixture was stirred to obtain N, N-dioctadecylanilineium tetrakis (pentafluorophenyl) borate and N, N-di.
• a uniform n-hexane solution of the composition containing octadecylaniline was obtained.
• the n-hexane was evaporated under reduced pressure and dried under reduced pressure at 50 ° C. to give the title composition.
• Example 2 It was confirmed that the composition obtained in Example 2 was dissolved in n-hexane at a concentration of 20% by weight.
• Example 3 Composition containing 2,6-di (nonadecil) pyridinium tetrakis (pentafluorophenyl) borate and 2,6-di (nonadecil) pyridine 2,6-di (nonadecil) pyridinium tetrakis (penta) obtained in Production Example 4.
• 2,6-di (nonadecil) pyridine (12.9 mg, 0.02 mmol) obtained in Production Example 2 to fluorophenyl) borate (129 mg, 0.1 mmol), and further add n-hexane (0.52 g). In addition, the mixture was stirred for 1 hour to obtain a uniform n-hexane solution.
• Example 3 It was confirmed that the composition obtained in Example 3 was dissolved in n-hexane at a concentration of 20% by weight.
• Example 4 Composition Containing 2-Nonadecyl-5-Octadecoxypyridinium Tetrakis (Pentafluorophenyl) Borate and 2-Nonadecyl-5-Octadecoxypyridine
• 2-Nonadecyl-5-octadecoxypyridine obtained in Production Example 6 (0.65 g, 1.1 mmol) and lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex (0.80 g, 0.88 mmol) were suspended in cyclohexane (20 mL), followed by a 1 M hydrogen chloride-diethyl ether solution.
• Example 4 It was confirmed that the composition obtained in Example 4 was dissolved in n-hexane at a concentration of 20% by weight.
• Example 5 Composition Containing 2-Nonadecyl-1-octadecylimidazole and 2-Nonadecyl-1-octadecylimidazolium Tetrakis (pentafluorophenyl) borate 2-Nonadecyl-1-octadecilimidazole (24.1 mg) obtained in Production Example 9. , 0.04 mmol) and 2-nonadecil-1-octadecylimidazolium tetrakis (pentafluorophenyl) borate (126.7 mg, 0.1 mmol) obtained in Production Example 11 were dissolved in cyclohexane (0.5 mL).
• Example 5 It was confirmed that the composition obtained in Example 5 was dissolved in cyclohexane at a concentration of 20% by weight.
• Example 6 Composition Containing 2-Heptadecyl-1-octadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate and 2-heptadecyl-1-octadecylbenzoimidazolium Tetrakis 2-heptadecyl-1-octadecilbenzoimidazolium tetrakis obtained in Production Example 13.
• Example 6 It was confirmed that the composition obtained in Example 6 was dissolved in n-hexane at a concentration of 10% by weight.
• Example 7 Composition Containing 2-Nonadecyl-5-Octadecoxypyridinium Tetrakis (Pentafluorophenyl) Borate and Tetradecyl Ether 2-Nonadecyl-5-Octadecoxypyridinium Tetrakis (Pentafluorophenyl) Borate (39 mg, 0.03 mmol) , Tetradecyl ether (12.3 mg, 0.03 mmol) and n-hexane (351 mg) were mixed and stirred at 25 ° C. The mixture became a homogeneous solution. The mixture was concentrated under reduced pressure and then dried under reduced pressure at 50 ° C. to give the title composition.
• Example 7 It was confirmed that the composition obtained in Example 7 was dissolved in n-hexane at a concentration of 10% by weight.
• Example 8 Composition containing 2,6-di (nonadecil) pyridinium tetrakis (pentafluorophenyl) borate and tetradecyl ether 2,6-di (nonadecil) pyridinium tetrakis (pentafluorophenyl) borate (39 mg) obtained in Production Example 4 , 0.03 mmol), tetradecyl ether (12.3 mg, 0.03 mmol) and n-hexane (351 mg) were mixed and stirred at 25 ° C. The mixture became a homogeneous solution. The mixture was concentrated under reduced pressure and then dried under reduced pressure at 50 ° C. to give the title composition.
• Example 8 It was confirmed that the composition obtained in Example 8 was dissolved in n-hexane at a concentration of 10% by weight.
• Example 9 Composition Containing 2-Heptadecyl-1-octadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate and tetradecyl ether 2-Heptadecyl-1-octadecylbenzoimidazolium tetrakis (pentafluorophenyl) borate obtained in Production Example 13 (39 mg, 0.03 mmol), tetradecyl ether (12.3 mg, 0.03 mmol) and n-hexane (351 mg) were mixed and stirred at 25 ° C. The mixture became a homogeneous solution.
• Example 9 It was confirmed that the composition obtained in Example 9 was dissolved in n-hexane at a concentration of 10% by weight.
• Example 10 Composition Containing 2-Nonadecyl-1-octadecylimidazolium Tetrakis (Pentafluorophenyl) Borate and Tetradecyl Ether 2-Nonadecyl-1-octadecil Imidazolium Tetrakis (Pentafluorophenyl) Borate (39 mg) obtained in Production Example 11 , 0.03 mmol), tetradecyl ether (73.8 mg, 0.15 mmol) and n-hexane (351 mg) were mixed and stirred at 25 ° C. The mixture became a homogeneous solution. The mixture was concentrated under reduced pressure and then dried under reduced pressure at 50 ° C.
• Example 10 It was confirmed that the composition obtained in Example 10 was dissolved in n-hexane at a concentration of 10% by weight.
• the compound obtained in Comparative Example 1 was sparingly soluble in n-hexane at a concentration of 20% by weight.
• the compound obtained in Comparative Example 2 was sparingly soluble in n-hexane at a concentration of 20% by weight.
• the compound obtained in Comparative Example 3 was sparingly soluble in n-hexane at a concentration of 20% by weight.
• the co-catalyst was dissolved in a solvent to prepare a co-catalyst solution having a predetermined concentration, which was transferred to a Schlenk tube.
• a solvent to prepare a co-catalyst solution having a predetermined concentration, which was transferred to a Schlenk tube.
• the total amount of the solvent and the total amount of triisobutylaluminum were adjusted to be constant.
• the catalyst solution and the co-catalyst solution are sequentially added to the autoclave, and immediately, the ethylene pressure is adjusted to a predetermined pressure and stirred at a predetermined temperature (25 ° C.) for a predetermined time. bottom.
• Table 1 shows the results of the polymerization reaction at 25 ° C. using various co-catalysts.
• composition of the present invention is soluble (or easily soluble) in a hydrocarbon solvent, particularly an aliphatic hydrocarbon solvent, and does not become a catalyst poison, so that it is useful as an auxiliary catalyst for polymerization of olefins and dienes.

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