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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
  • C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
  • C07D295/067—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents attached to the same carbon chain, which is not interrupted by carbocyclic rings
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  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor

Definitions

• the present invention relates to a fluorine-containing alkylammonium borate compound useful as an auxiliary catalyst for the polymerization of olefins, dienes and acetylenes, a composition containing the same, and a method for producing them.
• Non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for polymerization of olefins, dienes, and acetylenes.
• metallocene compounds such as metallocene compounds, diimine complexes, and phenoxy complexes
• phenoxy complexes as catalysts for polymerization of olefins, dienes, and acetylenes.
• cocatalysts used to stabilize the cationically active species of these metal complex catalysts alkylaluminum, aluminoxane such as methylaluminooxane (MAO), Bronsted acid salt such as ammonium borate, triphenylcarbenium borate and the like.
• Lewis acid salt is used (Non-Patent Document 1).
• Non-Patent Document 1 Bronsted acid containing nitrogen, phosphorus, oxygen, and / or sulfur is known (Patent Document 1).
• the Bronsted acid salt contains nitrogen such as dimethylanilinium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, and methylpyrrolidinium tetrakis (pentafluorophenyl) borate.
• Bronsted acid salt (ammonium borate) is known (Patent Document 2).
• a neutral amine compound is produced by losing protons at the protonation stage.
• Such a neutral amine compound may interact with the cationically active species of the metal complex catalyst, and in that case, there is a concern that the polymerization reaction may be adversely affected.
• N- (pentafluorophenyl) pyrrolidinium tetrakis (pentafluorophenyl) borate and the like have been proposed as co-catalysts in order to reduce the basicity of the neutral amine compound produced by the catalytic activation reaction (Patent Document 3). ..
• the present inventors have used a fluoroalkylammonium borate compound which exhibits higher polymerization activity as compared with the prior art as an auxiliary catalyst used in the polymerization reaction of olefin, diene and acetylene by a metal complex catalyst. It is an object of the present invention to provide the composition to be contained and the industrial manufacturing method thereof.
• 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 one or more fluoroC 1-4 alkyl groups.
• R 5 represents a C 1-30 alkyl group substituted with one or more substituents selected from the group consisting of a C 6-14 aryl group substituted with one or more fluorine atoms and a fluorine atom.
• R 6 and R 7 are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6-14 aryls, respectively.
• the compound represented by (hereinafter, also referred to as "the compound of the present invention") exhibits high metal complex catalytic activation ability in the polymerization reaction of olefin, diene and acetylene and is useful as a co-catalyst. , The present invention has been completed.
• 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 one or more fluoroC 1-4 alkyl groups.
• R 5 represents a C 1-30 alkyl group substituted with one or more substituents selected from the group consisting of a C 6-14 aryl group substituted with one or more fluorine atoms and a fluorine atom.
• R 6 and R 7 are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6-14 aryls, respectively.
• R 1 , R 2 , R 3 and R 4 are all pentafluorophenyl groups, 2, 2', 3, 3', 4', 5, 5', 6, 6'-nonafluoro-4- (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-
• the compound according to the above [1] which is a naphthyl group.
• R 5 is a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group or a fluoro C 1-6 alkyl group substituted with one or more fluorine atoms, respectively, the above-mentioned [1].
• R 6 and R 7 are independent of each other.
• C 6-14 aryl group which may be substituted with a halogen atom, A C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of (2) halogen atom and (3) C 1-30 alkoxy group; or (1) halogen atom, (2) C 1-30 alkyl group, (3) C 1-30 alkoxy group,
• the above-mentioned [1] which is a C 3-8 cycloalkyl group which may be substituted with a substituent selected from the group consisting of (4) halo C 1-30 alkyl group and (5) halo C 1-30 alkoxy group.
• [6] A 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocycle in which R 6 and R 7 are bonded to each other and may be substituted together with the nitrogen atom to which they are bonded.
• R 5 is a fluoroC 1-6 alkyl group, and R 6 and R 7 are independent of each other.
• composition of the present invention A composition containing a compound represented by (hereinafter, also referred to as "composition of the present invention"). [11] The composition according to the above [10], wherein R and R'are independent and optionally substituted C 1-30 alkyl groups. [12] The content of the compound represented by the formula (2) is in the range of 0.01 to 10 mol with respect to 1 mol of the compound represented by the formula (1). ] The composition according to.
• the content of the compound represented by the formula (2) is in the range of 0.1 to 3 mol with respect to 1 mol of the compound represented by the formula (1).
• the composition according to. [14] The compound according to any one of the above [1] to [9], and the following formula (3) :.
• a composition containing the compound represented by (however, in the composition, the compound represented by the formula (3) is an amine deprotonated from the cation constituting the formula (1) described in the above [1]. It is a compound.).
• Composition. [16] The above-mentioned [14], wherein the content of the compound represented by the formula (3) is in the range of 0.5 to 3 mol with respect to 1 mol of the compound represented by the formula (1).
• Composition. [17] Further, the following equation (2):
• 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 one or more fluoroC 1-4 alkyl groups.
• R5 is Represents (1) a C 6-14 aryl group substituted with one or more fluorine atoms and (2) a C 1-30 alkyl group substituted with one or more substituents selected from the group consisting of fluorine atoms.
• R 6 and R 7 are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6-14 aryls, respectively.
• a production method comprising a step of reacting with a compound represented by.
• a fluorine-containing alkylammonium borate compound which exhibits high metal complex catalytic activation ability and is useful as a co-catalyst in the polymerization reaction of olefin, diene and acetylene, a composition containing the compound, and their industrial products.
• a recipe can be provided.
• halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
• alkyl (group) means an alkyl group having 1 or more carbon atoms in a straight chain or a branched chain.
• 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 1-18 alkyl (group) means an alkyl group having 1 to 18 carbon atoms in a linear or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like.
• 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 1-30 alkyl (group) means a group in which one or more hydrogen atoms in the "C 1-30 alkyl” group are substituted with halogen atoms. Specifically, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl.
• the halogen atom in the "halo C 1-30 alkyl (group)" is a fluorine atom
• the C 1-30 alkyl group substituted with one or more fluorine atoms is "fluoro C 1-30 alkyl (fluoro C 1-30 alkyl).
• Basic 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 atoms. Specifically, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl.
• fluoroC 1-6 alkyl (group) include fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and penta.
• fluoroC 1-6 alkyl (group) in the definition of R5 include 2 -fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2, 2-Difluoropropyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2, FluoroC 1-6 alkyl (group) having a fluorine atom at the ⁇ -position and / or the ⁇ -position such as 2-difluoropentyl and 2,2-difluorohexyl is preferable, 2-fluoroethyl, 2,2-difluoroethyl and 2 , 2,2-Trifluoroethyl, pentafluoroethyl, 2,2-difluoropropy
• Substituents of C 6-14 aryl groups in R 1 , R 2 , R 3 and R 4 , or R 6 and R 7 are bonded to each other and formed together with the nitrogen atom to which they are bonded.
• Specific examples of "fluoroC 1-4 alkyl (group)" as a substituent of the cyclic group include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1-difluoroethyl and 2,2,2-trifluoroethyl.
• trifluoromethyl, 1,1-difluoroethyl, pentafluoroethyl, 1,1-difluoropropyl, heptafluoropropyl, 1,1-difluorobutyl and nonafluorobutyl are preferable, and trifluoromethyl and 1,1-difluoro Ethyl and pentafluoroethyl are more preferable.
• cycloalkyl (group) means a cyclic alkyl group, and is preferably a C 3-15 cycloalkyl group, more preferably a C 3-15 cycloalkyl group, unless the carbon number range is particularly limited. , C 3-8 cycloalkyl group.
• C 3-15 cycloalkyl (group) means a cyclic alkyl group having 3 to 15 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl. , Cyclodecyl, Cycloundecyl, Cyclododecyl, Cyclotridecyl, Cyclotetradecyl, Cyclopentadecyl and the like.
• 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. Of these, the C 3-6 cycloalkyl group is preferred.
• 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 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 1-30 alkoxy (group) means a group in which one or more hydrogen atoms in the "C 1-30 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.
• 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 C6-14 aryl groups such as 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl and 9-phenanthryl. Of these, phenyl, 4-biphenylyl, 1-naphthyl or 2-naphthyl are preferred.
• C 6-14 aryl (group) substituted with one or more fluorine atoms or one or more fluoroC 1-4 alkyl groups refers to the above-mentioned C 6-14 aryl group. It means a group in which one or more hydrogen atoms are substituted with a fluorine atom or a fluoroC 1-4 alkyl group, and specifically, for example, a pentafluorophenyl group, 2,2', 3,3', 4 ', 5,5', 6,6'-nonafluoro-4- (1,1'-biphenylyl) group, 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group, 1, Examples thereof include 3,4,5,6,7,8-heptafluoro-2-naphthyl group, 4-trifluoromethylphenyl group, 3,4-bis (trifluoromethyl) phenyl group and the like.
• 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 and 1,3,4,5,6,7,8-heptafluoro-2-naphthyl group are preferable.
• C 1-30 alkyl (group) substituted with a C 6-14 aryl group substituted with one or more fluorine atoms means one or more of the C 6-14 aryl groups.
• the hydrogen atom of is substituted with a C 1-30 alkyl group substituted with a group substituted with a fluorine atom, preferably substituted with a phenyl group or a naphthyl group substituted with one or more fluorine atoms, respectively. It is a C 1-6 alkyl group.
• a pentafluorophenylmethyl group 2,2', 3,3', 4', 5,5', 6,6'-nonafluoro-4- (1,1'-biphenylyl) methyl group.
• 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl group 1,3,4,5,6,7,8-heptafluoro-2-naphthylmethyl group and the like.
• pentafluorophenylmethyl group 2,3,4,5,6,7,8-heptafluoro-1-naphthylmethyl group or 1,3,4,5,6,7,8-heptafluoro-2.
• -A naphthylmethyl group is preferable, and a pentafluorophenylmethyl group is more preferable.
• the "cyclic group” formed by bonding R 6 and R 7 to each other together with the nitrogen atom to which they are bonded is a saturated nitrogen-containing non-aromatic heterocyclic group. It means a derived cyclic ammonio group (in the case of the compound of the present invention (compound (1))) or a saturated nitrogen-containing non-aromatic heterocycle (in the case of the compound (3) described later).
• the "cyclic ammonio group derived from a saturated nitrogen-containing non-aromatic heterocyclic group” means that R 6 and R 7 are bonded to each other and a hydrogen atom is bonded to the nitrogen atom to which they are bonded. Means a cyclic ammonio group formed by.
• the "cyclic group” may have a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to the carbon atom as another ring-constituting atom of the nitrogen atom of the amino group, and may have 3 to 8 members (3 to 8 members).
• a cyclic ammonio group derived from a monocyclic nitrogen-containing non-aromatic heteroatom group (preferably 4 to 6 members) can be mentioned.
• cyclic group examples include an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a pyrrolinyl group, a piperidyl group, an azepanyl group, a morpholinyl group, a thiomorpholinyl group, a piperazinyl group, an oxazolidinyl group, a thiazolidinyl group, an imidazolidinyl group, and an oxazolinyl group.
• Examples thereof include a cyclic ammonio group derived from a 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group such as a group, an imidazolinyl group, a pyrazoridinyl group, a pyrazolinyl group, a tetrahydropyridyl group, a tetrahydropyrimidinyl group and a tetrahydrotriazolyl group.
• a cyclic ammonio group derived from a 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocyclic group such as a group, an imidazolinyl group, a pyrazoridinyl group, a pyrazolinyl group, a tetrahydropyridyl group, a tetrahydropyrimidinyl group and a tetrahydrotriazolyl group.
• a cyclic ammonio group derived from an azetidinyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group or a morpholinyl group is preferable, and a cyclic ammonio group derived from a piperidyl group or a piperazinyl group is more preferable.
• the "saturated nitrogen-containing non-aromatic heterocycle” may have a heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to a carbon atom as another ring-constituting atom of the nitrogen atom of the amino group.
• Examples thereof include monocyclic nitrogen-containing non-aromatic heterocycles having 3 to 8 members (preferably 4 to 6 members).
• Specific examples of such a "saturated nitrogen-containing non-aromatic heterocycle” include aziridine, azetidine, pyrrolidine, pyrroline, piperidine, azepan, morpholine, thiomorpholin, piperazine, oxazolidine, thiazolidine, imidazolidine, oxazoline, thiazolin, imidazoline, and the like.
• Examples thereof include 3- to 8-membered monocyclic nitrogen-containing non-aromatic heterocycles such as pyrazolidine, pyrazoline, tetrahydropyridine, tetrahydropyrimidine, and tetrahydrotriazoline, among which azetidine, pyrrolidine, piperidine, piperazine or morpholine are preferable, and piperidine or Piperazine is more preferred.
• pyrazolidine such as pyrazolidine, pyrazoline, tetrahydropyridine, tetrahydropyrimidine, and tetrahydrotriazoline, among which azetidine, pyrrolidine, piperidine, piperazine or morpholine are preferable, and piperidine or Piperazine is more preferred.
• halogen atoms cyano groups, C 1-6 alkyl groups, halo C 1-6 alkyl groups, C 1-6 alkoxy groups, halo C 1-6 alkoxy groups or phenyl groups are preferable, and halogen atoms (eg, fluorine atoms).
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, trifluoromethyl, 2, 2, 2- Fluoro C 1-4 alkyl groups such as trifluoroethyl
• halo C 1-4 alkoxy groups eg, fluoro C 1-4 alkoxy groups such as trifluoromethoxy, 2,2,2-trifluoroethoxy
• 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.
• alkali metal ion examples include, for example, lithium ion, potassium ion, sodium ion, cesium ion and the like.
• alkaline earth metal ion examples include magnesium ion and calcium ion.
• 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 hydrocarbon solvent (or an aliphatic hydrocarbon solvent) and a compound (or composition) of the present invention at 25 ° C. It means that the compound (or composition) of the present invention dissolves in the solution of 5% by weight or more to form a transparent uniform solution.
• soluble in a hydrocarbon solvent or an aliphatic hydrocarbon solvent
• a compound (or composition) of the present invention dissolves in a concentration of 20% by weight or more (preferably 30% by weight or more) to form a transparent uniform solution.
• the compound of the present invention has the following formula (1):
• 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 one or more fluoroC 1-4 alkyl groups.
• R 5 represents a C 1-30 alkyl group substituted with one or more substituents selected from the group consisting of a C 6-14 aryl group substituted with one or more fluorine atoms and a fluorine atom.
• R 6 and R 7 are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6-14 aryls, respectively.
• R 1 , R 2 , R 3 and R 4 are preferably independently substituted with one or more fluorine atoms or one or more fluoroC 1-4 alkyl groups (eg, trifluoromethyl group).
• -A biphenylyl group particularly preferably a pentafluorophenyl group, 2,2', 3,3', 4', 5,5', 6 in which R 1 , R 2 , R 3 and R 4 are all the same.
• 6'-nonafluoro-4- (1,1'-biphenylyl) group 2,3,4,5,6,7,8-heptafluoro-1-naphthyl group or 1,3,4,5,6 It is a 7,8-heptafluoro-2-naphthyl group.
• R5 is preferably a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group, or a fluoro C 1-6 alkyl group substituted with one or more fluorine atoms, respectively, and more preferably.
• a phenylmethyl group eg, pentafluorophenylmethyl group
• fluoroC 1-6 alkyl group substituted with one or more fluorine atoms more preferably a fluoroC 1-6 alkyl group (eg, 2-fluoro).
• Fluoro C 1-6 alkyl group particularly preferably a fluoro C 1-4 alkyl group (eg, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl). , 2,2-Difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc. C 1-4 alkyl group).
• fluoro C 1-4 alkyl group eg, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl.
• R 6 and R 7 are preferably independent of each other.
• a C6-14 aryl group which may be substituted with a halogen atom (eg, a fluorine atom), It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• a halogen atom eg, a fluorine atom
• R 6 and R 7 may be attached to each other and substituted with the nitrogen atom to which they are attached 3-8.
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• a cyclic group derived from an azetidinyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group or a morpholinyl group, which may be substituted with a substituent of more choice, and particularly preferably R 6 and R 7 are bonded to each other. Then, together with the nitrogen atom to which they are bonded, a halogen atom (eg, fluorine atom), a C 1-4 alkyl group (eg, methyl, ethyl), and a C 1-4 alkoxy group (eg, methyl, ethyl), respectively.
• a halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methyl, ethyl
• halo C 1-4 alkyl group eg, a fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• a halo C 1-4 alkoxy group e.g. a fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• a halo C 1-4 alkoxy group e.g, a fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• the total carbon number of R 5 , R 6 and R 7 is preferably 25 or more, and more preferably 35 or more.
• N is preferably 1.
• M is preferably 1 or 2, and more preferably 1.
• Examples of the suitable compound (1) include the following compounds.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are independently one or more fluorine atoms or one or more fluoroC 1-4 alkyl groups (eg, trifluoromethyl group). ) Substituted with phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, respectively.
• R 5 is a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group, each substituted with one or more fluorine atoms, or a fluoro C 1-6 alkyl group (preferably 2, 2, 2- It is a fluoroC 2-4 alkyl group having a fluorine atom at the ⁇ -position such as trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and having 3 or more fluorine atoms).
• R 6 and R 7 are independent of each other.
• C 6-14 aryl group which may be substituted with a halogen atom, A C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of (2) halogen atom and (3) C 1-30 alkoxy group; or (1) halogen atom, (2) C 1-30 alkyl group, (3) C 1-30 alkoxy group, It is a C 3-8 cycloalkyl group which may be substituted with a substituent selected from the group consisting of (4) halo C 1-30 alkyl group and (5) halo C 1-30 alkoxy group.
• Compound (1) wherein n is 1 and m is 1.
• R 1 , R 2 , R 3 and R 4 in the formula (1) are independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups, respectively.
• a naphthyl group, a 2-naphthyl group or a 4-biphenylyl group, R 5 is a phenylmethyl group (eg, pentafluorophenylmethyl group) or fluoroC 1-6 alkyl group substituted with one or more fluorine atoms, more preferably a fluoroC 1-6 alkyl group (eg, eg).
• a C6-14 aryl group which may be substituted with a halogen atom (eg, a fluorine atom), It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• a halogen atom eg, a fluorine atom
• It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• 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, R 5 is a fluoroC 1-6 alkyl group (eg, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2).
• R 5 is a fluoroC 1-6 alkyl group (eg, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroeth
• a C6-14 aryl group which may be substituted with a halogen atom (eg, a fluorine atom), It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• a halogen atom eg, a fluorine atom
• It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• 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, R 5 is a fluoroC 1-4 alkyl group (eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2).
• R 5 is a fluoroC 1-4 alkyl group (eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl
• R 6 and R 7 are independent of each other.
• a C6-14 aryl group which may be substituted with a halogen atom (eg, a fluorine atom), It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• a halogen atom eg, a fluorine atom
• It is a C 1-30 alkyl group that may be substituted with a substituent selected from the group consisting of (2) a halogen atom and (3) a C 1-30 alkoxy group.
• R 1 , R 2 , R 3 and R 4 in the above formula (1) are independently one or more fluorine atoms or one or more fluoroC 1-4 alkyl groups (eg, trifluoromethyl group). ) Substituted with phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 3 -Phenyltril group or 9-Phenyltril group, R 5 is a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group, each substituted with one or more fluorine atoms, or a fluoro C 1-6 alkyl group (preferably 2, 2, 2- It is a fluoroC 2-4 alkyl group having a fluorine atom at the ⁇ -position such
• R 1 , R 2 , R 3 and R 4 in the formula (1) are independently substituted with one or more fluorine atoms or one or more trifluoromethyl groups, respectively.
• a naphthyl group, a 2-naphthyl group or a 4-biphenylyl group, R 5 is a phenylmethyl group (eg, pentafluorophenylmethyl group) or fluoroC 1-6 alkyl group substituted with one or more fluorine atoms, more preferably a fluoroC 1-6 alkyl group (eg, eg).
• Fluoro C 1-6 alkyl groups having a fluorine atom can be mentioned, and among them, having a fluorine atom at the ⁇ -position such as 2,2,2-trifluoroethyl and 2,2,3,3,3-pentafluoropropyl. , And a fluoroC 2-4 alkyl group having 3 or more fluorine atoms is preferable).
• R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, respectively.
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• 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, R 5 is a fluoroC 1-6 alkyl group (eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2).
• R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, respectively.
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group Forming a cyclic group derived from a piperidyl group or a piperazinyl group, which may be substituted with a more selected substituent, Compound (1), wherein n is 1 and m is 1 or 2.
• 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, R 5 is a fluoroC 1-4 alkyl group (eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2).
• R 5 is a fluoroC 1-4 alkyl group (eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• Compound (1) wherein n is 1 and m is 1.
• Preferred specific examples of the compound (1) include, for example, the compounds of Examples 1, 4 to 21, 23, and 25 described later.
• composition of the present invention Hereinafter, the composition of the present invention will be described.
• composition of the present invention comprises the compound (1) (compound of the present invention) and the following formula (2):
• composition containing the compound (1) and the compound (2) is not particularly limited as long as it contains both compounds, and the compound in which the compound (2) is coordinated with the compound (1) to form a complex is used. It may be included.
• the composition of the present invention is preferably a composition containing a complex formed by the compound (1) and the compound (2).
• R and R' are independently substituted C 1-30 alkyl groups, optionally substituted C 3-15 cycloalkyl groups or optionally substituted C 6-14 aryl groups, respectively. And preferably, each independently (1) Halogen atom, A C 1-30 alkyl group which 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; (1) Halogen atom, (2) C 1-30 alkyl group, (3) C 1-30 alkoxy group, A C 3-15 cycloalkyl group optionally substituted with a substituent selected from the group consisting of (4) halo C 1-30 alkyl group and (5) halo C 1-30 alkoxy group; or (1) halogen.
• a C 1-30 alkyl group a C 3-8 cycloalkyl group (eg, cyclopentyl, cyclohexyl, etc.); or (1) a halogen atom, (2) C 1-6 alkyl group, (3) C 1-6 alkoxy group, It is a phenyl group which may be substituted with a substituent selected from the group consisting of (4) halo C 1-6 alkyl group and (5) halo C 1-6 alkoxy group, and more preferably each independently.
• C 1-30 alkyl group (preferably C 1-18 alkyl group such as methyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like).
• Preferred specific examples of the compound (2) include, for example, dibutyl ether, dihexyl ether, dioctyl ether, didecyl ether, didodecyl ether, ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, cyclopentylmethyl ether, diphenyl ether, and the like. Examples thereof include phenyl octadecyl ether.
• the content of compound (2) with respect to 1 mol of compound (1) is preferably in the range of 0.01 to 10 mol, more preferably in the range of 0.1 to 3 mol. Is.
• compositions of the present invention include, for example, the compositions of Examples 2, 3, 24, 26 to 34 described later.
• a preferred embodiment of compound (3) is the compound, except that it deprotonates when R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded to form a cyclic group. This is the same as the preferred embodiment of each group (R 5 , R 6 and R 7 ) in (1).
• Examples of the suitable compound (3) include the following compounds.
• R 5 in the formula (3) is a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group substituted with one or more fluorine atoms, respectively, or a fluoro C 1-6 alkyl group (preferably). , 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc. Fluoro C 2-4 alkyl having a fluorine atom at the ⁇ -position and having 3 or more fluorine atoms It is a group), and R 6 and R 7 are independent of each other.
• C 6-14 aryl group which may be substituted with a halogen atom, A C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of (2) halogen atom and (3) C 1-30 alkoxy group; or (1) halogen atom, (2) C 1-30 alkyl group, (3) C 1-30 alkoxy group, Compound (3) a compound (3) which is a C 3-8 cycloalkyl group which may be substituted with a substituent selected from the group consisting of (4) halo C 1-30 alkyl group and (5) halo C 1-30 alkoxy group. ).
• R 5 in the formula (3) is a phenylmethyl group (eg, pentafluorophenylmethyl group) substituted with one or more fluorine atoms or a fluoroC 1-6 alkyl group, more preferably fluoroC.
• Alkyl groups eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetra ⁇ such as fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.
• 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetra ⁇ such as fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-diflu
• Fluoro C 1-6 alkyl groups having a fluorine atom at the position and / or ⁇ position can be mentioned, among which ⁇ such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like.
• ⁇ such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like.
• a fluoroC 2-4 alkyl group having a fluorine atom at the position and having three or more fluorine atoms is preferable), and R 6 and R 7 are independent of each other.
• a halogen atom eg, a fluorine atom
• Compound (3) which is a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of (2) halogen atom and (3) C 1-30 alkoxy group.
• R 5 in the formula (3) is a fluoroC 1-6 alkyl group (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2).
• 3, 3,3-Pentafluoropropyl, etc. is preferably a fluoroC 2-4 alkyl group having a fluorine atom at the ⁇ -position and having 3 or more fluorine atoms), and R 6 and R 7 .
• R 6 and R 7 each independently (1) A C6-14 aryl group which may be substituted with a halogen atom (eg, a fluorine atom), Compound (3), which is a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of (2) halogen atom and (3) C 1-30 alkoxy group.
• R 5 in the formula (3) is a fluoroC 1-4 alkyl group (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2).
• -Fluoro C 1-4 having a fluorine atom at the ⁇ -position such as difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.
• Alkyl groups are mentioned, and among them, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like have a fluorine atom at the ⁇ -position and have three or more fluorine atoms.
• Compound (3) which is a C 1-30 alkyl group optionally substituted with a substituent selected from the group consisting of a halogen atom and a C 1-30 alkoxy group.
• R 5 in the formula (3) is a C 1-6 alkyl group substituted with a phenyl group or a naphthyl group substituted with one or more fluorine atoms, respectively, or a fluoro C 1-6 alkyl group (preferably). , 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, etc. Fluoro C 2-4 alkyl having a fluorine atom at the ⁇ -position and having 3 or more fluorine atoms It is a group.) And contains a 3- to 8-membered monocyclic structure in which R 6 and R 7 are bonded to each other and may be substituted together with the nitrogen atom to which they are bonded. A compound (3) that forms a nitrogen non-aromatic heterocycle.
• R 5 in the formula (3) is a phenylmethyl group (eg, pentafluorophenylmethyl group) substituted with one or more fluorine atoms or a fluoroC 1-6 alkyl group, more preferably fluoroC.
• Alkyl groups eg 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetra ⁇ such as fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, etc.
• 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2-difluoropropyl, 2,2,3,3-tetra ⁇ such as fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-diflu
• Fluoro C 1-6 alkyl groups having a fluorine atom at the position and / or ⁇ position can be mentioned, among which ⁇ such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like.
• ⁇ such as 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like.
• a fluoroC 2-4 alkyl group having a fluorine atom at the position and having three or more fluorine atoms is preferable), and R 6 and R 7 are bonded to each other, and they are bonded to each other.
• each (1) Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• R 5 in the formula (3) is a fluoroC 1-6 alkyl group (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2).
• 3, 3,3-Pentafluoropropyl, etc. is preferably a fluoroC 2-4 alkyl group having a fluorine atom at the ⁇ -position and having 3 or more fluorine atoms), and R 6 and R 7 .
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• Compound (3) which forms piperidine or piperazine, which may be substituted with a of more selected substituents.
• R 5 in the formula (3) is a fluoroC 1-4 alkyl group (for example, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 2,2).
• -Fluoro C 1-4 having a fluorine atom at the ⁇ -position such as difluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2-difluorobutyl, etc.
• Alkyl groups are mentioned, and among them, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl and the like have a fluorine atom at the ⁇ -position and have three or more fluorine atoms. Fluoro C 2-4 alkyl group having is preferable), and R 6 and R 7 are bonded to each other and together with the nitrogen atom to which they are bonded, respectively.
• Halogen atom eg, fluorine atom
• C 1-4 alkyl group eg, methyl, ethyl
• C 1-4 alkoxy group eg, methoxy, ethoxy
• halo C 1-4 alkyl group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• halo C 1-4 alkoxy group eg, fluoro C 1-4 alkyl group such as trifluoromethyl, 2,2,2-trifluoroethyl
• a compound (3) that forms a piperidine which may be substituted with a more selected substituent.
• Preferred specific examples of the compound (3) include, for example, a fluorine-containing alkylamine used for synthesizing the compounds of Examples 1 and 4 to 21 described later, a fluorine-containing alkyl cyclic amine, and the like.
• the content of the compound (3) with respect to 1 mol of the compound (1) is preferably in the range of 0.01 to 10 mol. More preferably, it is in the range of 0.5 to 3 mol.
• composition of the present invention containing the compound (1) and the compound (3) include, for example, the composition of Example 22 described later.
• composition of the present invention containing the compound (1) and the compound (3) may further contain the compound (2) in addition to the compound (1) and the compound (3).
• the preferred embodiment of the compound (2) that may be further contained is the same as the preferred embodiment of each group (R and R') in the compound (2) and the preferred specific examples thereof. Further, in the composition of the present invention containing the compound (1), the compound (2) and the compound (3), the contents of the compound (2) and the compound (3) with respect to 1 mol of the compound (1) are as described above. Is similar to.
• the aliphatic hydrocarbon at room temperature 15 to 30 ° C.
• conventionally known borate-type compounds for example, hydrogenated tetrakis (pentafluorophenyl) borate, hydrocarbonated tetrakis (pentafluorophenyl) borate diethyl ether complex, lithium tetrakis (pentafluorophenyl) borate, etc.
• borate-type compounds for example, hydrogenated tetrakis (pentafluorophenyl) borate, hydrocarbonated tetrakis (pentafluorophenyl) borate diethyl ether complex, lithium tetrakis (pentafluorophenyl) borate, etc.
• a known borate compound is usually used in a polymerization reaction as a solution of an aromatic hydrocarbon solvent, but as a result, it is necessary to remove the contaminated aromatic hydrocarbon solvent, which is commercially available as the number of steps increases. There is a problem that it costs a lot of money. Further, although it may be used in a polymerization reaction as a suspension of an aliphatic hydrocarbon solvent, there are problems such as poor operability due to the suspension and a problem that an excessive amount is required.
• the compound or composition of the present invention which is soluble in an aliphatic hydrocarbon solvent, assists in the polymerization reaction of homogeneous olefins, dienes and acetylenes using a hydrocarbon solvent (particularly, an aliphatic hydrocarbon solvent). Especially useful as a catalyst.
• the method for producing the compound (or composition) of the present invention is not particularly limited, but can be produced, for example, according to the following production methods 1 to 3, or the method described in Production Examples or Examples described later.
• a fluorine-containing alkylamine by the following production method, it is possible to obtain the compound (or composition) of the present invention with a simpler operation, lower cost and higher yield as compared with the conventional method. Therefore, it can be an industrial manufacturing method.
• the production method 1 is a step of obtaining the compound (7) by reacting the dialkylamine compound (5) and the fluoroalkylcarboxylic acid anhydride (6) in a solvent that does not affect the reaction in the presence of a base (step 1).
• step (step 3) of obtaining the compound (1a) (the compound of the present invention) by reacting the compound (3a) with the compound (4) is included.
• R 8 is a C 1-29 alkyl group substituted with one or more substituents selected from the group consisting of a C 6-14 aryl group substituted with one or more fluorine atoms and a fluorine atom.
• substituents selected from the group consisting of a C 6-14 aryl group substituted with one or more fluorine atoms and a fluorine atom.
• the definition of each other symbol is synonymous with the above.
• Solvents used in this step include hydrocarbon solvents such as toluene, n-hexane, isohexane, n-heptane, n-octane, cyclohexane and methylcyclohexane; ethers such as diethyl ether and tetrahydrofuran; chloroform, dichloromethane and the like. Halogen-based solvents; or a mixed solvent thereof can be mentioned, and among them, a mixed solvent of toluene-tetrahexane is preferable.
• the amount of the compound (6) used is usually 1 to 3 mol, preferably 1 to 2 mol, and more preferably 1.2 mol with respect to 1 mol of the compound (5).
• Examples of the base used in this step include organic bases such as triethylamine, N, N-diisopropylethylamine, pyridine and 2,6-lutidine, and among them, triethylamine is preferable.
• the amount of the base used is usually 1 to 3 mol, preferably 1 to 2 mol, and more preferably 1.2 mol with respect to 1 mol of the compound (5).
• 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 reaction time is usually about 10 minutes to 10 hours, preferably 30 minutes to 30 minutes. It takes about 2 hours.
• the compound (7) prepared as described above can be used as it is in the step 2.
• the solvent used in this step is not particularly limited, and examples thereof include ethers such as triglyme, tetrahydrofuran, tetrahydropyran, and dioxane, and among them, tetrahydrofuran is preferable.
• Examples of the reducing agent used in this step include boron-based hydrides and aluminum-based hydrides.
• Specific examples of the reducing agent are not particularly limited, but are, for example, sodium borohydride, lithium borohydride, aluminum lithium borohydride, borane-tetrahexyl complex, borane-dimethylsulfide complex, sodium borohydride / iodine, and hydrogenation.
• Examples thereof include sodium boron / trifluoroacetic acid, and among them, boron-based hydrides such as borane-tetrahexyl complex, borane-dimethylsulfide complex, sodium borohydride / iodine, and sodium borohydride / trifluoroacetic acid are preferable.
• the amount of the reducing agent used such as borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, sodium borohydride / iodine, sodium borohydride / trifluoroacetic acid, is usually 2 to 10 mol per 1 mol of compound (7). It is preferably 2 to 3 mol.
• the reaction temperature is the reflux temperature of the solvent usually used, and is preferably 40 ° C to 80 ° C.
• the reaction time is usually about 30 minutes to 10 hours, preferably about 1 to 4 hours.
• the solvent used in this step is not particularly limited, but is, for example, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, trichloroethylene, toluene, n-hexane, isohexane, n-heptane, n-.
• halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, trichloroethylene, toluene, n-hexane, isohexane, n-heptane, n-.
• Hydrocarbon-based solvents such as octane, cyclohexane, and methylcyclohexane are mentioned, and among them, dichloromethane, chloroform, n-hexane, isohexane, n-heptane, cyclohexane, methylcyclohexane and the like are preferable, and dichloroethane, chloroform, n-hexane, isohexane, n. -Heptane or methylcyclohexane are particularly preferred.
• Examples of the acid used in this step include protonic acids such as hydrogen bromide, hydrogen chloride, and hydrogen iodide, and hydrogen chloride is preferable.
• hydrogen chloride a commercially available product (1.0 M hydrogen chloride-diethyl ether solution or hydrochloric acid) can be used as it is.
• the amount of the acid used is usually 1 to 5 mol, preferably 1 to 2 mol, relative to 1 mol of compound (3a).
• the compound (4) used in this step is not particularly limited, but a commercially available product or a refined product may be used, or a compound prepared by a method known per se may be used.
• Specific examples of the compound (4) include, for example, lithium tetrakis (pentafluorophenyl) borate, potassium tetrakis (pentafluorophenyl) borate, lithium tetrakis (heptafluoronaphthyl) borate, potassium tetrakis (heptafluoronaphthyl) borate, and chloromagnesium.
• Tetrakis (pentafluorophenyl) borate, chloromagnesium tetrakis (heptafluoronaphthyl) borate, bromomagnesium tetrakis (pentafluorophenyl) borate, bromomagnesium tetrakis (heptafluoronaphthyl) borate, lithium tetrakis (nonafluorobiphenyl) borate, potassium tetrakis ( Nonafluorobiphenyl) borate, chloromagnesium tetrakis (nonafluorobiphenylyl) borate, bromomagnesium tetrakis (nonafluorobiphenyl) borate, lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex, lithium tetrakis (pentafluorophenyl) borate (1) diethyl ether complex and the like
• the reaction temperature is usually 0 ° C. to 80 ° C., preferably 15 ° C. to 60 ° C., and the reaction time is usually about 10 minutes to 10 hours, preferably about 1 to 3 hours.
• composition of the present invention containing the compound (1a) and the compound (2) by carrying out in the presence of the compound represented by (compound (2)). It can be carried out in the same manner as in step 3 of the above-mentioned production method 1 except that the compound (2) is added.
• the amount of compound (2) used is usually 0.01 to 10 mol, preferably 0.1 to 3 mol, relative to 1 mol of compound (4).
• a composition containing the compound (1a) and the compound (3a) (the composition of the present invention) is obtained by using an excess amount of the compound (3a) in the reaction of the step 3 of the above-mentioned production method 1.
• the method It can be carried out in the same manner as in step 3 of the above-mentioned production method 1 except that an excess amount of the compound (3a) is used.
• the amount of compound (3a) used is usually 1.01 to 11 mol, preferably 1.1 to 4 mol, relative to 1 mol of compound (4).
• the compound of the present invention (compound (1)) or the composition of the present invention is a compound or composition derived from a fluorine-containing alkylamine, it is a compound that can be a catalytic poison such as an amine compound having high basicity and nucleophilicity. Is substantially free of. Therefore, it is useful as an auxiliary catalyst for polymerization of olefins, dienes and acetylenes.
• the present invention comprises using the compound of the present invention (compound (1)) or the composition of the present invention as a co-catalyst to polymerize at least one monomer selected from the group consisting of olefins, dienes and acetylenes. , Includes methods for producing polymers.
• % Indicates mol / mol% for the yield, and indicates weight% for the others unless otherwise specified. Further, the room temperature means a temperature of 15 ° C to 30 ° C unless otherwise specified.
• the solvents and reagents used in the following examples are Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Junsei Chemical Co., Ltd., Kanto Chemical Co., Inc., Combi Blocks Co., Ltd. Purchased from a distributor such as.
• the deuterated solvent used for NMR measurement was purchased from the Cambridge Isotope Laboratory. The following equipment was used for the analysis. 1 1 H-NMR and 19 F-NMR: 400YH manufactured by JEOL Ltd.
• Example 1 Synthesis of N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate N, N-dioctadecyl-2,2,2-trifluoroethylamine hydrochloride obtained in Production Example 3 Dissolve salt (0.32 g, 0.5 mmol) in chloroform (30 mL), add lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex (0.45 g, 0.5 mmol), and stir at room temperature for 1 hour. did. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure.
• Example 2 Synthesis of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and ditetradecyl ether N, N-dioctadecyl- obtained in Example 1
• the title composition was prepared by mixing 2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate (0.30 g, 0.22 mmol) with ditetradecyl ether (0.09 g, 0.22 mmol). Obtained.
• N-hexane was added to the composition obtained in Example 2 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Isohexane was added to the composition obtained in Example 2 to prepare a 20% by weight isohexane solution, and it was confirmed that the solution was uniform.
• N-heptane was added to the composition obtained in Example 2 to prepare a 20 wt% n-heptane solution, and it was confirmed that the solution was uniform.
• ISOPAR E (registered trademark) was added to the composition obtained in Example 2 to prepare a 20 wt% ISOPAR E (registered trademark) solution, and it was confirmed that the solution was uniform.
• Cyclohexane was added to the composition obtained in Example 2 to prepare a 20% by weight cyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the composition obtained in Example 2 to prepare a 20% by weight methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Example 3 Synthesis of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and dibutyl ether N, N-dioctadecyl-2, obtained in Example 1
• the title composition was obtained by mixing 2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate (300 mg, 0.23 mmol) and dibutyl ether (62 mg, 0.46 mmol).
• Example 3 It was confirmed that the composition obtained in Example 3 was dissolved in n-hexane in an amount of 30% by weight.
• Example 5 Synthesis of N-benzyl-N-methyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate N-benzyl-N-methyl-2,2,2-trifluoro obtained in Production Example 5
• Ethylamine hydrochloride (0.30 g, 1.25 mmol) is dissolved in chloroform (30 mL), lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex (1.10 g, 1.21 mol) is added, and at room temperature, 1 Stirred for hours. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure.
• the insoluble material was collected by filtration.
• the insoluble matter was dissolved in water and dichloromethane, and the organic layer was separated.
• the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the title compound (0.65 g, 65%).
• Methylcyclohexane was added to the compound of Example 7 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Example 8 Synthesis of N, N-dicyclohexyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate N, N-dicyclohexyl-2,2,2-trifluoroethylamine hydrochloride obtained in Production Example 12 ( 0.33 g, 1.1 mmol) was dissolved in chloroform (30 mL), lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex (1.0 g, 1.1 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure.
• Methylcyclohexane was added to the compound of Example 11 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Example 12 Synthesis of N, N-Dioctyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate N, N-dioctyl-2,2,2-trifluoroethylamine hydrochloride obtained in Production Example 20 ( 0.50 g, 1.39 mmol) was dissolved in chloroform (10 mL), lithium tetrakis (pentafluorophenyl) borate tridiethyl ether complex (1.25 g, 1.38 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure.
• Methylcyclohexane was added to the compound of Example 13 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the compound of Example 14 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the compound of Example 16 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the compound of Example 17 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the compound of Example 19 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform. It was
• Methylcyclohexane was added to the compound of Example 20 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Pentafluorophenyl) borate tridiethyl ether complex (0.91 g, 1 mmol) was added. The reaction mixture was stirred at room temperature for 1 hour. After washing the mixture with water, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure at 45 ° C. to give the title compound (1.20 g, 74%).
• Methylcyclohexane was added to the compound of Example 21 to prepare a 10 wt% methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Example 22 Production Example of Production of Composition Containing N, N-Dioctadecyl-2,2,2-Trifluoroethylammonium Tetrakiss (Pentafluorophenyl) Borate and N, N-Dioctadecyl-2,2,2-Trifluoroethylamine
• N, N-dioctadecyl-2,2,2-trifluoroethylamine (0.90 g, 1.49 mmol) obtained in 2 was dissolved in chloroform (30 mL), and lithium tetrakis (pentafluorophenyl) borate tridiethyl ether was dissolved.
• N-Hexane was added to the composition of Example 22 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Isohexane was added to the composition of Example 22 to prepare a 20% by weight isohexane solution, and it was confirmed that the solution was uniform.
• N-heptane was added to the composition of Example 22 to prepare a 20 wt% n-heptane solution, and it was confirmed that the solution was uniform.
• ISOPAR E registered trademark
• Example 22 was added to the composition of Example 22 to prepare a 20 wt% ISOPAR E (registered trademark) solution, and it was confirmed that the solution was uniform.
• Cyclohexane was added to the composition of Example 22 to prepare a 20 wt% cyclohexane solution, and it was confirmed that the solution was uniform.
• Methylcyclohexane was added to the composition of Example 22 to prepare a 20% by weight methylcyclohexane solution, and it was confirmed that the solution was uniform.
• Cyclohexane was added to Example 23 to prepare a 20 wt% cyclohexane solution, and it was confirmed that the solution was uniform.
• Example 24 Preparation of Composition Containing N, N-Ditetradecyl-2,2,2-Trifluoroethylammonium Tetrakis (Pentafluorophenyl) Borate and Didodecyl Ether N, N-Ditetradecyl-2,2 obtained in Example 23 , 2-Trifluoroethylammonium Tetrakis (pentafluorophenyl) borate (58 mg, 0.05 mmol) and dodecyl ether (40 mg, 0.10 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 24 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Cyclohexane was added to the compound of Example 25 to prepare a 20 wt% cyclohexane solution, and it was confirmed that the solution was uniform.
• Example 26 Preparation of composition containing N, N-dihexadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and dihexadecyl ether N, N-dihexadecyl-2, obtained in Example 25. 2,2-Trifluoroethylammonium tetrakis (pentafluorophenyl) borate (60 mg, 0.05 mmol) and dihexadecyl ether (23 mg, 0.05 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 26 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 27 Preparation of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and dioctyl ether N, N-dioctadecyl-2, obtained in Example 1 2,2-Trifluoroethylammonium tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and dioctyl ether (12 mg, 0.05 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 27 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 28 Preparation of Composition Containing N, N-Dioctadecyl-2,2,2-Trifluoroethylammonium Tetrakis (Pentafluorophenyl) Borate and Didodecyl Ether N, N-Dioctadecyl-2 obtained in Example 1 , 2,2-Trifluoroethylammonium Tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and dodecyl ether (15 mg, 0.05 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 28 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 29 Preparation of Composition Containing N, N-Dioctadecyl-2,2,2-Trifluoroethylammonium Tetrakis (Pentafluorophenyl) Borate and Dihexadecyl Ether N, N-Dioctadecyl- obtained in Example 1 2,2,2-Trifluoroethylammonium tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and dihexadecyl ether (23 mg, 0.05 mmol) were added and mixed to obtain the title composition. ..
• N-Hexane was added to the composition of Example 29 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 30 Preparation of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and diphenyl ether N, N-dioctadecyl-2,2 obtained in Example 1 , 2-Trifluoroethylammonium Tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and diphenyl ether (8.5 mg, 0.05 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 30 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 31 Preparation of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and octadecylphenyl ether N, N-dioctadecyl-2 obtained in Example 1 , 2,2-Trifluoroethylammonium Tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and octadecylphenyl ether (18 mg, 0.05 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 31 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 32 Preparation of composition containing N, N-dioctadecyl-2,2,2-trifluoroethylammonium tetrakis (pentafluorophenyl) borate and cyclopentyl methyl ether N, N-dioctadecyl-2 obtained in Example 1 , 2,2-Trifluoroethylammonium Tetrakis (pentafluorophenyl) borate (64 mg, 0.05 mmol) and cyclopentyl methyl ether (10 mg, 0.10 mmol) were added and mixed to obtain the title composition.
• N-Hexane was added to the composition of Example 32 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 33 Production of Composition Containing N, N-Dihexadecyl-2,2,2-Trifluoroethylammonium Tetrakis (Pentafluorophenyl) Borate and Ditetradecyl Ether N, N-Dihexadecyl-2, obtained in Production Example 40.
• 2,2-Trifluoroethylamine hydrochloride (8.10 g, 13.9 mmol) is dissolved in dichloromethane (80 mL), ditetradecyl ether (8.10 g, 13.9 mmol) and lithium tetrakis (pentafluorophenyl) borate 3.
• N-hexane was added to the composition obtained in Example 33 to prepare a 20 wt% n-hexane solution, and it was confirmed that the solution was uniform.
• Example 34 Preparation of Composition Containing N, N-Dihexadecyl-2,2,2-Trifluoroethylammonium Tetrakiss (Pentafluorophenyl) Borate and Didodecyl Ether N, N-Dihexadecyl-2,2 obtained in Example 25. , 2-Trifluoroethylammonium tetrakis (pentafluorophenyl) borate (439.2 mg, 0.36 mmol), and dodecyl ether (254 mg, 0.72 mmol) are mixed and n-hexane (1.756 g) is added. To prepare a uniform hexane solution of the title composition.
• 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 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 predetermined at a predetermined temperature (25 ° C or 100 ° C). Stirred for hours.
• the fluorine-containing ammonium borate compounds of Examples 1, 2, 4, 7, 11 and 22 do not contain a fluorine atom, regardless of the polymerization temperature and the type of solvent used. It was confirmed that the polymerization activity was higher than that of the compound of Comparative Example 2. Further, as shown in Table 1, in the composition (or complex) of the present invention (Examples 1, 2, 4 and 22), a polymer having a melting point lower than that of the comparative example can be obtained depending on the polymerization conditions, and the comonomer can be incorporated. It is believed that the amount is increasing.
• the compound or composition of the present invention exhibits high metal complex catalytic activation ability in the polymerization reaction of olefin, diene and acetylene, and is useful as a co-catalyst. Further, according to the present invention, an industrial method for producing a compound or composition of the present invention can also be provided.

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