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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
  • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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  • C07D233/54—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
  • 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
  • C07D233/58—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 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F4/00—Polymerisation catalysts
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  • 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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  • 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
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  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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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 borate compound useful as an auxiliary catalyst for the polymerization of olefins and diene, and a method for producing them.
• Non-metallocene metal complex catalysts such as metallocene compounds, diimine complexes, and phenoxy complexes as catalysts for the polymerization of olefins and dienes.
• aluminoxane such as alkylaluminum and methylaluminooxane
• 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).
• amine compounds are produced by losing protons at the protonation stage.
• Such an 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.
• a non-polar hydrocarbon solvent is used as the solvent used in the polymerization.
• the switch to an aliphatic hydrocarbon solvent such as n-hexane is progressing rather than an aromatic hydrocarbon solvent such as toluene.
• Patent Document 4 Di (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate and bis (hydrogenated beef alkyl) methylammonium tetrakis (pentafluorophenyl) borate described in Patent Document 4 are useful as compounds soluble in a hydrocarbon solvent. ..
• the present invention is to provide a borate compound which is soluble in a hydrocarbon solvent and useful as an auxiliary catalyst for a polymerization reaction of an olefin or a diene, and an industrial production 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 fluoroC 1-4 alkyl groups.
• a + -H is a 5- or 6-membered monocyclic nitrogen-containing group having 25 or more total carbon atoms substituted with two or more identical or different C 1-30 alkyl groups or C 1-30 alkoxy groups. Represents a cation in which the ring nitrogen atom of an aromatic heterocyclic compound is protonated.
• the compound represented by does not generate a compound that is a catalyst poison for the polymerization reaction of olefin or diene, and is useful as an auxiliary catalyst for the polymerization reaction of olefin or diene. For the first time, I found this and came to complete the present invention.
• 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 fluoroC 1-4 alkyl groups.
• a + -H is a 5- or 6-membered monocyclic nitrogen-containing group having 25 or more total carbon atoms substituted with two or more identical or different C 1-30 alkyl groups or C 1-30 alkoxy groups. Represents a cation in which the ring nitrogen atom of an aromatic heterocyclic compound is protonated.
• 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-
• the compound according to the above [1] which is a naphthyl group.
• a polymer comprising polymerizing at least one monomer selected from the group consisting of olefins and dienes using the compound according to any one of [1] to [5] above as a co-catalyst. Production method.
• the borate compound which is soluble in a hydrocarbon solvent and useful as an auxiliary catalyst for a polymerization reaction of an olefin or a diene.
• 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 linear or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl.
• C 9-30 alkyl (group) means an alkyl group having 9 to 30 carbon atoms in a linear or branched chain, and for example, nonadecylic, decyl, undecyl, dodecyl, tridecylic, tetradecyl. , Hexadecyl, octadecyl, nonadecylic, eikosyl, docosyl, tridecylic, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonadecylic, triacoylic acid 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, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl. , Se-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. Can be mentioned. 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 Alternatively, 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 for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. 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, and the like.
• Examples thereof include luoxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, triacoxyloxy and
• 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, and the like.
• Tridecyloxy, Tetradecyloxy, Hexadecyloxy, Octadecyloxy, Nonadesyloxy, Eikosyloxy, Docosyloxy, Tricosyloxy, Tetracosyloxy, Pentacosyloxy, Hexacosyloxy, Heptacosyloxy, Octacosyl Oxy, nonacosyloxy, triacoxyloxy and the like can be mentioned.
• 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, and the like. Examples thereof include isobutoxy, sec-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.
• fluoroC 1-4 alkoxy (group) is preferable, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy.
• pentafluoroethoxy is more preferable, and trifluoromethoxy is particularly preferable.
• 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, 1-naphthyl or 2-naphthyl is preferred.
• the "5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound” refers to 1 to 4 heteros 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 5- or 6-membered monocyclic aromatic heterocyclic compound containing an atom, and means a compound containing at least one nitrogen atom as a ring-constituting atom.
• Suitable examples of the "5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound” include, for example, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isooxazole, pyridine, pyrazine, pyrimidine, pyridazine. , 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, triazole, tetrazole, triazine and the like, among which pyridine Alternatively, imidazole is more 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, heptane, octane, cyclohexane, methylcyclohexane, and a mixed solvent thereof.
• soluble in a hydrocarbon solvent means that the compound of the present invention is dissolved at a concentration of 5% by weight or more in a solution of the hydrocarbon solvent and the compound of the present invention at 25 ° C. and is transparent. Means to form a uniform solution of.
• 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 fluoroC 1-4 alkyl groups.
• a + -H is a 5- or 6-membered monocyclic nitrogen-containing group having 25 or more total carbon atoms substituted with two or more identical or different C 1-30 alkyl groups or C 1-30 alkoxy groups. Represents a cation in which the ring nitrogen atom of an aromatic heterocyclic compound is protonated.
• It is a compound represented by.
• A a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound (eg, pyrrole, imidazole) substituted with two identical or different C 9-30 alkyl groups or C 9-30 alkoxy groups.
• a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound eg, pyrrole, imidazole substituted with two identical or different C 9-30 alkyl groups or C 9-30 alkoxy groups.
• pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiazole, 1 , 3,4-Thiazylazole, triazole, tetrazole, triazine, etc. are preferred, and pyridine or imidazole substituted with two identical or different C 14-30 alkyl groups or C 14-30 alkoxy groups is more preferred.
• the total carbon number of A is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more.
• Preferred specific examples of A include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecil-5-octadecylpyridine, 2-nonadecil-4-octadecyloxypyridine, 2-nonadecil.
• Examples thereof include -6-octadecyloxypyridine, 4-nonadecil-1-octadecylimidazole, 5-nonadecil-1-octadecylimidazole, 2-nonadecil-1-octadecylimidazole and the like.
• the group represented by is represented by a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic group, X'represents a halogen atom, and R 5 is a optionally substituted C 1-30 alkyl group. Represents, and n1 represents an integer of 2 or more.
• the compound (a2) is obtained by reacting the compound (a1) with a phosphonium salt ( R5 - CH2PPh3X ') in the presence of a base in a solvent that does not affect the reaction. (Step 1), A can be produced by the reaction with the reducing agent (step 2).
• 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 (a1).
• the amount of the phosphonium salt (R 5 -CH 2 PPh 3 X') used is also 1 to 2 mol (preferably 1 to 1 mol) with respect to the equivalent amount (1 mol) of the formyl group of the compound (a1). 2 mol).
• the reaction solvent in step 1 is not particularly limited, but is, for example, an ether solvent such as tetrahydrofuran and diethoxyethane, an aromatic hydrocarbon solvent such as toluene, an aliphatic hydrocarbon solvent such as n-hexane, dimethylformamide and dimethyl. Sulfoxide and the like are preferred.
• 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 or 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 the equivalent amount (1 mol) of the double bond of the compound (a2).
• the reaction solvent in step 2 is not particularly limited, but for example, n-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 1 hour to 72 hours.
• R 1 , R 2 , R 3 and R 4 are preferably independently substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups (eg, trifluoromethyl group), phenyl.
• R2 , R3 and R4 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.
• 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 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, 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-octadecylimidazole, Alternatively, the 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-oct
• Preferred specific examples of the compound (1) include, for example, 2,6-dinonadecylpyridinium tetrakis (pentafluorophenyl) borate, 2-nonadecil-5-octadecyloxypyridinium tetrakis (pentafluorophenyl) borate, 4-nonadecil-.
• Examples thereof include 1-octadecyl imidazolium tetrakis (pentafluorophenyl) borate, 5-nonadecil-1-octadecyl imidazolium tetrakis (pentafluorophenyl) borate, 2-nonadecil-1-octadecil imidazolium tetrakis (pentafluorophenyl) borate and the like. ..
• the compound of the present invention is soluble in a hydrocarbon solvent at room temperature (15 to 30 ° C.). Further, the conventionally known borate-type co-catalyst is insoluble in an aliphatic hydrocarbon solvent such as n-hexane, whereas the compound of the present invention is also soluble in an aliphatic hydrocarbon solvent. It is useful as a co-catalyst for the polymerization reaction of homogeneous olefins and dienes.
• the compound 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 (pentafluoro)). It is preferable that it does not contain phenyl) 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 the 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 is as follows:
• R 1 , R 2 , R 3 and R 4 in the equation are synonymous with the above.
• Examples of the compound (3) used as a raw material in this 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, hydrogenated [3,5-bis (trifluoromethyl) phenyl] bolate and the like 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 a C 6-14 aryl group substituted with one or more fluorine atoms or fluoroC 1-4 alkyl groups.
• 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) may be used.
• the solvent used in the production of the compound (3) is not particularly limited, but is an ether solvent such as diethyl ether, tert-butylmethyl ether, cyclopentylmethyl ether and diisopropyl ether, and halogen-based solvents such as dichloromethane and chloroform. It is desirable to use an aromatic hydrocarbon solvent such as toluene and benzene, and an aliphatic hydrocarbon solvent such as n-hexane, isohexane, heptane, octane, cyclohexane and methylcyclohexane. Further, these solvents may be used alone or in combination.
• the protonic acid used when treating the compound (4) is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, hydrogen bromide acid, and hydrogen iodide acid.
• the amount of the protonic acid used in the production of the compound (3) is an equimolar amount (1 to 1.01 mol, preferably 1 mol) with respect to 1 mol of the compound (4). Is desirable.
• 1 mol or more of protonic acid it is preferable to wash the organic phase with water until the pH of the aqueous phase after washing becomes 3 or more so that the protonic acid used does not remain in the organic phase after treatment.
• the pH of the aqueous phase is less than 3, the protonate used for the organic phase remains, and in the subsequent reaction with A, the protonate of 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 A.
• the A used in the production method of the present invention is a 5- or 6-membered monocyclic nitrogen-containing aromatic heterocyclic compound having a total carbon number of 25 or more (preferably 30 or more, more preferably 35 or more). Can be mentioned. Specific examples of A include, for example, 2,5-dinonadecylpyridine, 2,6-dinonadecylpyridine, 2-nonadecil-5-octadecylpyridine, 2-nonadecil-4-octadecyloxypyridine, 2-nonadecil-.
• Examples thereof include 6-octadecyloxypyridine, 4-nonadecil-1-octadecylimidazole, 5-nonadecil-1-octadecylimidazole, 2-nonadecil-1-octadecylimidazole and the like.
• the compound (1) obtained by the reaction with A having a total carbon number of 25 or more (2) is also soluble in a hydrocarbon solvent.
• the reaction temperature and time in the production method of the present invention are not particularly limited, but the reaction temperature is usually 0 ° C to 40 ° C, preferably 10 to 35 ° C, and more preferably room temperature (15 to 30 ° C). , The time is 10 minutes or more.
• reaction solution is dehydrated with a desiccant such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and then the solvent is removed to obtain 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 compound (1-1) to the compound (1-3)).
• a salt of A and a protonic acid for example, a hydrochloride of A
• a protonic acid for example, a hydrochloride of A
• an equimolar amount of the salt and the compound (4) are mixed in a solvent and stirred.
• a solution of the compound (1) can be obtained.
• the types of protonic acid and solvent, reaction temperature, reaction time, etc. are based on the above-mentioned production method of the present invention.
• 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 above formula (4) are independently substituted with one or more fluorine atoms or trifluoromethyl groups, phenyl group, 1-naphthyl group or 2-naphthyl group, 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 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, 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.
• the compound of the present invention is a compound that is soluble in a hydrocarbon solvent and can be a catalytic poison such as an amine compound having high basicity and nucleophilicity, a protonate salt thereof, and an ether compound having a total carbon number of 7 or less. Does not contain. Therefore, it is useful as an auxiliary catalyst for polymerization of olefins and diene.
• 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 compound of the present invention as a co-catalyst.
• the production of a polymer using the compound of the present invention as a co-catalyst can be carried out according to the method described in the test example described later.
• % 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.
• Example 1 It was confirmed that the compound obtained in Example 1 was dissolved in methylcyclohexane at a concentration of 10% by weight.
• Example 2 Synthesis of 2-Nonadecyl-5-octadecoxypyridinium tetrakis (pentafluorophenyl) borate 2-Nonadecyl-5-octadecoxypyridine hydrochloride (0.25 g, 0.38 mmol) and lithium tetrakis obtained in Production Example 6 (Pentafluorophenyl) borate Diethyl ether complex (0.29 g, 0.38 mmol) was suspended in cyclohexane (50 mL), and the mixture was stirred at room temperature for 1 hour.
• Example 2 It was confirmed that the compound obtained in Example 2 was dissolved in methylcyclohexane at a concentration of 10% by weight.
• Example 3 Synthesis of 2-Nonadecyl-1-octadecylimidazolium tetrakis (pentafluorophenyl) borate 2-Nonadecyl-1-octadecyimidazole hydrochloride (0.98 g, 1.57 mmol) and lithium tetrakis (pentafluoropentafluoro) obtained in Production Example 10 After suspending the phenyl) borate diethyl ether complex (1.19 g, 1.57 mmol) in cyclohexane (30 mL), the mixture was stirred at room temperature for 1 hour.
• Example 3 It was confirmed that the compound obtained in Example 3 was dissolved in methylcyclohexane at a concentration of 10% by weight.
• 1-octene, triisobutylaluminum (TIBA, 0.55 Mn-hexane solution) and a solvent methylcyclohexane (MCH)
• TIBA triisobutylaluminum
• MCH methylcyclohexane
• a polymerization catalyst dimethylsilylene (tert-butylamide)-(tetramethylcyclopentadienyl) -titanium (IV) -dichloride (CGC)
• triisobutylaluminum (0.55 Mn-hexane solution) and a solvent were added and determined in advance.
• a catalytic solution of concentration was prepared and transferred to a Schlenk tube.
• the co-catalyst was dissolved in a solvent to prepare a co-catalyst solution having a predetermined concentration, and the solution was transferred to a Schlenk tube. During the reaction after mixing the comonomer solution, the catalyst solution, and the co-catalyst solution, the total amount of the solvent and the total amount of triisobutylaluminum were adjusted to be constant. After purging the inside of the autoclave with ethylene gas, the catalyst solution and the 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. did.
• Table 1 shows the results of the polymerization reaction at 25 ° C. using various co-catalysts.
• N, N-dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate obtained by a method known per se (see, for example, US Pat. No. 6,221,185) was used.
• the compound of the present invention is soluble in a hydrocarbon solvent and does not become a catalyst poison, it is useful as an auxiliary catalyst for polymerization of olefins and dienes.

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