WO2012111778A1 - Catalyseur de polymérisation d'oléfines et procédé de production de polymère oléfinique - Google Patents

Catalyseur de polymérisation d'oléfines et procédé de production de polymère oléfinique Download PDF

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WO2012111778A1
WO2012111778A1 PCT/JP2012/053729 JP2012053729W WO2012111778A1 WO 2012111778 A1 WO2012111778 A1 WO 2012111778A1 JP 2012053729 W JP2012053729 W JP 2012053729W WO 2012111778 A1 WO2012111778 A1 WO 2012111778A1
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group
carbon atoms
tert
mmol
butyl
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正行 長谷川
並河　正明
正人 ▲高▼野
伊藤　和幸
昭彦 石井
憲男 中田
智之 戸田
史彦 河内
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住友化学株式会社
国立大学法人埼玉大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the present invention relates to a catalyst for olefin polymerization using a zirconium complex and a method for producing an olefin polymer.
  • metallocene catalysts has been one of the topics in the chemistry of olefin polymerization that has been greatly developed by Ziegler-Natta type magnesium-supported highly active titanium catalysts. Further, recently, development of so-called post metallocene catalysts has attracted attention as a catalyst for constructing a more precise polymerization process.
  • Patent Document 1 reports propylene polymerization using a diphenoxytitanium complex, a zirconium complex or a hafnium complex derived from ethane-1,2-dithiol, but it is improved from the viewpoint of stereoregularity of the resulting polymer. There is room for.
  • Non-patent Document 1 diphenoxytitanium complex, zirconium complex and hafnium complex derived from trans-cyclooctane-1,2-dithiol have been reported (Non-patent Document 1), and among these complexes, zirconium complex was used as a catalyst. -Hexene polymerization has also been reported (Non-Patent Document 2).
  • the problem to be solved by the present invention is an olefin polymerization catalyst capable of producing a polymer obtained by polymerizing an olefin having 3 to 10 carbon atoms (excluding 1-hexene) with excellent stereoregularity. And providing a method for producing an olefin polymer using the olefin polymerization catalyst.
  • the present inventor has found that the above-mentioned problems can be solved by intensive studies.
  • the present invention relates to a catalyst for olefin polymerization having 3 to 10 carbon atoms, wherein a complex represented by the following general formula (1) and an activating co-catalyst component are contacted (however, 1-hexene homopolymerization) Except for catalysts for use).
  • R 1 and R 5 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Or a substituted silyl group is represented.
  • R 2 to R 4 and R 6 to R 12 are each independently a hydrogen atom, a halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An alkynyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Substituted silyl groups, Alternatively, it represents a heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the alkynyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic compound in R 1 to R 12 The residue may have a substituent.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 9 And R 10 , and R 11 and R 12 may be independently connected to each other to form a ring, and these rings may have a substituent.
  • X is independently a hydrogen atom, a halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An alkenyl group having 2 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Substituted silyl groups, A substituted amino group, It represents a substituted thiolate group or a carboxylate group having 1 to 20 carbon atoms.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the aralkyl group, the aryl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the carboxylate group in X may have a substituent. Good. Adjacent Xs may be connected to each other to form a ring. L represents a neutral Lewis base. When there are a plurality of L, the plurality of L may be the same or different. l is 0, 1, or 2. ) Moreover, this invention relates to the manufacturing method of the olefin homopolymer or copolymer using the said catalyst.
  • a polymer obtained by polymerizing an olefin having 3 to 10 carbon atoms (excluding 1-hexene) can be produced with excellent stereoregularity.
  • R 1 and R 5 are preferably each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aralkyloxy group having 7 to 30 carbon atoms, An aryloxy group having 6 to 30 carbon atoms or a substituted silyl group, More preferably, each independently A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, Or a substituted silyl group, More preferably, each independently, A halogen atom, An alkyl group having 5 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring,
  • R 1 and R 5 are the same, An alkyl group having 5 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, Or it is a substituted silyl group.
  • R 2 to R 4 and R 6 to R 8 are preferably each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, Or a substituted silyl group, More preferably, each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, Or it is a substituted silyl group.
  • R 2 , R 4 , R 6 and R 8 are more preferably a hydrogen atom. More preferably as R 3 and R 7 , A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, Or a substituted silyl group, Most preferably, An alkyl group having 1 to 20 carbon atoms.
  • R 3 and R 7 are the same, A cycloalkyl group having 3 to 10 carbon atoms constituting an alkyl group ring having 1 to 20 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, Or a substituted silyl group, Most preferably, An alkyl group having 1 to 20 carbon atoms.
  • R 9 to R 12 are preferably each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, A substituted silyl group, More preferably, each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring, An aralkyl group having 7 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, Or a substituted silyl group, More preferably, each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 10 carbon atoms constituting the ring
  • alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, and aryloxy group may have a substituent.
  • Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 1 to R 12 include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro group.
  • a tertiary amine having 4 to 8 carbon atoms such as a tert-butyl group, a tert-pentyl group or a texyl group.
  • a kill group Most preferably, it is a tertiary alkyl group having 5 to 8 carbon atoms such as a tert-pentyl group or a texyl group.
  • the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms in R 2 to R 4 and R 6 to R 12 is preferably a perfluoromethyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, n-hexyl group, texyl group, neohexyl group, n-heptyl group, n
  • An alkyl group having 4 to 10 carbon atoms such as an octyl group and an n-decyl group, more preferably a perfluoromethyl group, a methyl group, an isopropyl group, an isobutyl group, a ter
  • Examples of the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms constituting the ring in R 1 to R 12 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms in R 1 to R 12 include vinyl group, allyl group, propenyl group, 2-methyl-2-propenyl group, homoallyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, a decenyl group and the like can be mentioned.
  • An alkenyl group having 3 to 6 carbon atoms is preferable, and an allyl group and a homoallyl group are more preferable.
  • Examples of the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms in R 1 to R 12 include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, and a 3-methyl-1-butynyl group.
  • Examples of the substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms in R 1 to R 12 include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methyl Phenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, ( 3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2, 3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-te Lamethylphenyl) methyl group,
  • Examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms in R 2 to R 4 and R 6 to R 12 include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, 2 , 3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetra Methylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropy
  • Examples of the substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms in R 1 to R 12 include a perfluoromethoxy group, a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoroisopropoxy group, a perfluoro group, Fluoro-n-butoxy group, perfluoro-sec-butoxy group, perfluoroisobutoxy group, perfluoro-n-pentyloxy group, perfluoronepentyloxy group, perfluoro-n-hexyloxy group, perfluoro-n -Heptyloxy group, perfluoro-n-octyloxy group, perfluoro-n-decyloxy group, perfluoro-n-dodecyloxy group, perfluoro-n-pentadecyloxy group, perfluoro-n-eicosyloxy group Methoxy group, ethoxy group,
  • Examples of the substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms in R 1 to R 12 include, for example, phenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2, 3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetra Methylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, 2,6-diisopropylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, pentafluoro Phenoxy group, 2-trifluoromethylphenoxy group, 3-trifluoromethylphenoxy group, 4-trifluoro Methylphenoxy group, 2,3-difluorophenoxy group, 2,4-fluorophenoxy group, 2,5-difluorophenoxy group
  • Examples of the substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms in R 1 to R 12 include, for example, benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) Ny
  • Examples of the substituted or unsubstituted heterocyclic compound residue having 3 to 20 carbon atoms constituting the ring in R 2 to R 4 and R 6 to R 12 include a thienyl group, a furyl group, and a 1-pyrrolyl group.
  • 1-imidazolyl group 1-pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, dibenzo-1H-pyrrol-1-yl group, Preferred are thienyl group, furyl group, 1-pyrrolyl group, pyridyl group, pyrimidinyl group, 2-isoindolyl group, 1-indolyl group, quinolyl group, and dibenzo-1H-pyrrol-1-yl group.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , and R 7 and R 8 are Each independently may be linked to each other to form a ring, and the ring may have a substituent, and is preferably a 4- to 10-membered hydrocyclic hydrocarbon containing two carbon atoms on the benzene ring. It is a carbyl ring or a heterocyclic ring, and the ring may have a substituent.
  • the ring include cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, benzene ring or naphthalene ring, furan ring, 2,5-dimethylfuran ring, thiophene ring, 2, 5-dimethylthiophene ring, pyridine ring and the like can be mentioned, and preferred are cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, benzene ring or naphthalene ring, and more preferred are R 1 and R 2 , and R 5.
  • R 6 are a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a benzene ring and a naphthalene ring
  • R 9 and R 10 , and R 11 and R 12 may be independently connected to each other to form a ring, and the ring has a substituent. You may do it.
  • An aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a substituted silyl group are represented by R 2 to R 4. And the same groups as those described above for R 6 to R 12 .
  • Examples of the substituted amino group in X include 2 to 14 carbon atoms such as dimethylamino group, diethylamino group, di-n-butylamino group, di-n-propylamino group, diisopropylamino group, dibenzylamino group, or diphenylamino group. And a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, or a dibenzylamino group.
  • Examples of the substituted thiolate group in X include a thiophenoxy group, 2,3,4-trimethylthiophenoxy group, 2,3,5-trimethylthiophenoxy group, 2,3,6-trimethylthiophenoxy group, 2,4 , 6-trimethylthiophenoxy group, 3,4,5-trimethylthiophenoxy group, 2,3,4,5-tetramethylthiophenoxy group, 2,3,4,6-tetramethylthiophenoxy group, 2,3,5 , 6-tetramethylphenoxy group, pentamethylphenoxy group, 2-fluorothiophenoxy group, 3-fluorothiophenoxy group, 4-fluorophenoxy group, pentafluorothiophenoxy group, 2-trifluoromethylthiophenoxy group, 3-tri Fluoromethylthiophenoxy group, 4-trifluoromethylthiophenoxy group, 2, -Difluorothiophenoxy group, 2,4-fluorothiophenoxy group, 2,5-difluorothiophenoxy group, 2-chloro
  • Examples of the substituted or unsubstituted carboxylate group having 1 to 20 carbon atoms in X include an acetate group, propionate group, butyrate group, pentanate group, hexanoate group, 2-ethylhexanoate group or trifluoroacetate group.
  • Preferred are hydrocarbyl carboxylate groups having 2 to 10 carbon atoms, and more preferred are acetate groups, propionate groups, 2-ethylhexanoate groups or trifluoroacetate groups.
  • X is preferably a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
  • An amino group particularly preferably a chlorine atom, a methyl group, a benzyl group, an isopropoxy group, a phenoxy group, a dimethylamino group, and most preferably, a chlorine atom, a benzyl group.
  • R 1 to R 12 and X may each independently have a substituent containing a halogen atom, an oxygen atom, a silicon atom, a nitrogen atom, a phosphorus atom, or a sulfur atom.
  • L represents a neutral Lewis base. When there are a plurality of L, the plurality of L may be the same or different. l is 0, 1, or 2.
  • L examples include ethers, amines or thioethers, and specific examples include tetrahydrofuran, diethyl ether, 1,4-dioxane, and pyridine. L is preferably tetrahydrofuran.
  • L is preferably 1 or 0, more preferably 0.
  • the benzyl group directly bonded to the zirconium atom of these compounds was changed to a chlorine atom, a methyl group, a dimethylamino group, an isopropoxy group, a tert-butoxy group, or a phenoxy group. Also included are compounds.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • Preferred examples of the complex (1) include the following compounds.
  • More preferable examples of the complex (1) include the following compounds.
  • the compound which changed the group corresponded to R ⁇ 3 > and R ⁇ 7 > of said each compound into the methyl group can also be mentioned, for example.
  • the following compounds are most preferable.
  • the compound which changed the group corresponded to R ⁇ 3 > and R ⁇ 7 > of said each compound into the methyl group can also be mentioned, for example.
  • the complex represented by the general formula (1) can be synthesized, for example, by the method described in Non-Patent Document 2, and specifically, the compounds represented by the general formulas (2) and (3) are used as starting materials. However, it should not be limited to this method.
  • X in the compound (3) is the same as X in the general formula (1).
  • the ZrX 4 for example, Zr (CH 2 Ph) 4 , ZrCl 2 (CH 2 Ph) 2, Zr (CH 2 SiMe 3) 4, ZrF 4, Zr Cl 4, ZrBr 4, ZrI 4, Zr (OMe) 4 , Zr (OEt) 4 , Zr (Oi-Pr) 4 , ZrCl 2 (Oi-Pr) 2 , Zr (On-Bu) 4 , Zr (Oi-Bu) 4 , Zr (Ot-Bu) 4 , Zr (OPh) 4 , Zr (NMe 2 ) 4 , ZrCl 2 (NMe 2 ) 2 , Zr (NEt 2 ) 4 may be mentioned.
  • the compound (2) and the compound (3) may be reacted as they are, or the compound (3) may be reacted after reacting the compound (2) with a base as necessary.
  • the base to be used include an organic lithium reagent, a Grignard reagent, and a metal hydride. Specifically, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexahexide are used.
  • Mention may be made of methyldisilazane, potassium hexamethyldisilazane, sodium hydride or potassium hydride, preferably n-butyllithium, lithium diisopropylamide, potassium hexamethyldisilazane, sodium hydride or potassium hydride. .
  • the reaction can be carried out under dehydration and deoxygenation. preferable. Specifically, it is under dry nitrogen or dry argon.
  • the amount of the compound (2) used may be 1 molar equivalent or more with respect to the compound (3), and preferably 1.0 to 1.5 molar equivalents. Moreover, when the compound (2) remains in the course of the reaction, the compound (3) may be added during the reaction.
  • the temperature at which compound (2) and compound (3) are reacted is in the temperature range of ⁇ 100 ° C. to 150 ° C., preferably in the temperature range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
  • the reaction of the compound (2) and the compound (3) may be carried out until the time when the yield of the product becomes the highest, preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours.
  • the temperature at which the compound (2) reacts with the base is in the temperature range of ⁇ 100 ° C. to 150 ° C., preferably in the temperature range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
  • the reaction time of the compound (2) and the base may be carried out until the product yield becomes the highest, and is 5 minutes to 24 hours, preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.
  • the reaction time of the compound produced by reacting the compound (2) with the base and the compound (3) may be the time until the yield of the product becomes the highest, and is 5 minutes to 48 hours. Preferably, it is 10 minutes to 24 hours.
  • the solvent to be used is not particularly limited as long as it is a solvent generally used in similar reactions, and examples thereof include a hydrocarbon solvent or an ether solvent.
  • Preferred is toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether or tetrahydrofuran, and more preferred is diethyl ether, toluene, tetrahydrofuran, hexane, pentane, heptane. Or cyclohexane.
  • Compound (2) can be synthesized, for example, according to the method described in Non-Patent Document 2. Specifically, although it can manufacture by the following scheme 2, it should not be limited to this method. Hereinafter, each process will be described in detail.
  • X ′ represents an anionic leaving group, for example, halogen atom, acetate group, trifluoroacetate group, benzoate group, CF 3 SO 3 group, CH 3 SO 3 group, 4-MeC 6 H 4 SO 3 group or PhSO 3 A group such as a chlorine atom, a bromine atom, an iodine atom, a CF 3 SO 3 group, a CH 3 SO 3 group, a 4-MeC 6 H 4 SO 3 group or a PhSO 3 group.
  • the base is not particularly limited, but includes inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium carbonate, and amine bases such as triethylamine and triisobutylamine. An amine base is preferred.
  • This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen.
  • it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.
  • the compound (6) may be purified as necessary.
  • a purification method for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt.
  • the purity can be increased by a purification operation such as distillation, recrystallization or silica gel chromatography.
  • Compound (2) can be synthesized by reacting compound (6) with 1.0 to 4.0 equivalents, preferably 1.0 to 1.5 equivalents of compound (7) in the presence of a base.
  • the base examples include inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium carbonate, and amine bases such as triethylamine and triisobutylamine, with amine bases being preferred.
  • inorganic bases such as potassium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and calcium carbonate
  • amine bases such as triethylamine and triisobutylamine, with amine bases being preferred.
  • This reaction can be performed in an atmosphere of air, helium, argon, or nitrogen.
  • it is under a helium, argon or nitrogen atmosphere, more preferably under a nitrogen or argon atmosphere.
  • the compound (2) may be purified as necessary.
  • a purification method for example, an ammonium chloride aqueous solution, a hydrochloric acid aqueous solution or a sodium chloride aqueous solution is added to the reaction solution, followed by addition of ethyl acetate or diethyl ether, and an extraction operation is performed to remove excess base or salt.
  • the purity can be increased by a purification operation such as distillation, recrystallization or silica gel chromatography.
  • the compound (2) can also be obtained by reacting the compound (6) and the compound (7) produced in the reactor by controlling the reaction conditions of [step 1].
  • R 1 is the same as R 5
  • R 2 is the same as R 6
  • R 3 is the same as R 7
  • R 4 is the same as R 8
  • the combination of R 9 and R 10 is R
  • the compound (2) can also be synthesized by reacting preferably 2.0 to 4.0 equivalents in the presence of a base.
  • Specific examples of the compound (2) include the following compounds.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • R 3 or a hydrogen atom the corresponding group R 7 in these compounds, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or also be mentioned compounds substituted with a methyl group, it can.
  • Examples thereof also include compounds in which the groups corresponding to R 9 to R 12 in each of the above compounds are substituted with a methyl group or an ethyl group.
  • the complex represented by the general formula (1) described above is used as a catalyst component for polymerization in producing a polymer by homopolymerization of olefin or copolymerization of two or more polymerizable olefins, preferably Is a catalyst component for homopolymerization (excluding the catalyst component for 1-hexene homopolymerization).
  • the polymerization catalyst a polymerization catalyst obtained by bringing the complex represented by the complex (1) into contact with the promoter component (A) is used.
  • the promoter component (A) include an activation promoter component containing a group 13 element in the periodic table, for example, There may be mentioned at least one compound selected from the group consisting of (A-1) an organoaluminum compound and (A-2) a boron compound.
  • organoaluminum compound (A-1) As the organoaluminum compound (A-1) used in the present invention, a known organoaluminum compound can be used.
  • (A-1-1) an organoaluminum compound represented by the general formula E 1 a AlY 1 3-a , (A-1-2) a general formula ⁇ —Al (E 2 ) —O— ⁇ b
  • Y 1 represents a hydrogen atom or a halogen atom, and all Y 1 may be the same or different, a is an integer of 0 ⁇ a ⁇ 3, b is an integer of 2 or more, and c is 1 or more. Any one of them, or a mixture of 2 to 3 thereof.
  • organoaluminum compound (A-1-1) represented by the general formula E 1 a AlY 1 3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and the like.
  • Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, etc.
  • Alkyl aluminum dichloride dimethyl aluminum Um hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
  • Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.
  • E 2 and E 3 in the linear aluminoxane (A-1-3) having the structure represented by 2 are methyl group, ethyl group, n-propyl group, isopropyl group, normal butyl group, Examples of the alkyl group include an isobutyl group, an n-pentyl group, and a neopentyl group.
  • b is an integer of 2 or more
  • c is an integer of 1 or more.
  • E 2 and E 3 are a methyl group and an isobutyl group
  • b is an integer of 2 to 40
  • c is an integer of 1 to 40.
  • aluminoxane can be made by various methods. There is no restriction
  • an aluminoxane is prepared by bringing a solution obtained by dissolving a trialkylaluminum (such as trimethylaluminum) into an appropriate organic solvent (such as benzene, toluene, or aliphatic hydrocarbon) into contact with water.
  • a trialkylaluminum such as trimethylaluminum
  • an appropriate organic solvent such as benzene, toluene, or aliphatic hydrocarbon
  • the method of making aluminoxane by making trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.
  • the linear aluminoxane having a structure represented by E 3 ⁇ —Al (E 3 ) —O— ⁇ c AlE 3 2 may be used after distilling off the volatile components if necessary.
  • the compound obtained by distilling off the volatile components and drying may be washed with an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.), and dried again for use.
  • the boron compound (A-2) includes (A-2-1) a boron compound represented by the general formula BR 13 R 14 R 15 , (A-2-2) a general formula W + (BR 13 R 14 R 15 R 16 ) — or a boron compound represented by (A-2-3) general formula (VH) + (BR 13 R 14 R 15 R 16 ) — Use.
  • B is a trivalent boron atom
  • R 13 to R 15 are halogen atoms, 1 to 20 Hydrocarbyl group containing 1 to 20 carbon atoms, halogenated hydrocarbyl group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms Or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different.
  • Preferred R 13 to R 15 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • boron compound (A-2-1) examples include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4). , 5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like. Most preferred are triphenylborane and tris (pentafluorophenyl) borane.
  • W + is an inorganic or organic cation
  • B is a trivalent valence state.
  • R 13 to R 16 are the same as R 13 to R 15 in the boron compound (A-2-1). That is, R 13 to R 16 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
  • a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
  • Preferred R 13 to R 16 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • W + that is an inorganic cation examples include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation.
  • W + that is an organic cation examples include a triphenylcarbenium cation. (BR 13 R 14 R 15 R 16 ) — includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro).
  • Phenyl) borate tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.
  • Specific examples of the compound represented by the general formula W + (BR 13 R 14 R 15 R 16 ) — include ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium tetrakis (pentafluoro).
  • Phenyl) borate silver tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-bistrifluoromethylphenyl) borate, etc.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferable.
  • R 13 to R 16 are the same as R 13 to R 15 in the boron compound (A-2-3). is there. That is, R 13 to R 16 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
  • a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
  • Preferred R 13 to R 16 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
  • Examples of (VH) + that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like (BR 13 R 14 R 15 R 16 ) ⁇ Is the same as described above.
  • Specific examples of the compound represented by the general formula (VH) + (BR 13 R 14 R 15 R 16 ) ⁇ include triethylammonium tetrakis (pentafluorophenyl) borate and tripropylammonium tetrakis (pentafluorophenyl) borate.
  • the contact between the complex (1) and the cocatalyst component is as follows.
  • any means may be used.
  • the complex (1) and the promoter component (A) may be mixed with the solvent (1) without being diluted in advance with a solvent. It is possible to employ a method of contacting, or a method of separately supplying the complex (1) and the promoter component (A) to the polymerization tank and bringing them into contact with each other in the polymerization tank.
  • the co-catalyst component (A) may be used in combination of a plurality of types, but some of them may be mixed in advance or used separately by supplying them to the polymerization tank. May be.
  • the complex (1) an isolated one may be used, or a compound obtained by contacting the compound (2) and the compound (3) may be used as it is.
  • each component used is usually such that the molar ratio of the organoaluminum compound (A-1) to the complex represented by the general formula (1) is 0.01 to 10,000, preferably 1 to 5,000. Further, each component is used so that the molar ratio of the boron compound (A-2) to the complex represented by the general formula (1) is 0.01 to 100, preferably 1.0 to 50. Is desirable.
  • the concentration when each component is supplied in a solution state or suspended or slurried in a solvent is determined depending on the performance of the apparatus for supplying each component to the polymerization reactor, etc.
  • the complex represented by the general formula (1) is usually 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L, and still more preferably, 0.01 to 100 mmol / L
  • the organoaluminum compound (A-1) in terms of Al atom is usually 0.01 to 10000 mmol / L, more preferably 0.05 to 5000 mmol / L, still more preferably 0.1 to 2000 mmol / L
  • the boron compound (A-2) is usually 0.001 to 500 mmol / L, more preferably 0.01 ⁇ 250 mmol / L, more preferably, it is desirable to use each component to be in the range of 0.05 ⁇ 100mmol / L.
  • the olefin polymerization catalyst is an olefin polymerization obtained by contacting the complex represented by the general formula (1) with the organoaluminum compound (A-1) and / or the boron compound (A-2).
  • the organoaluminum compound (A-1) is used as an organoaluminum compound (A-1) Is preferably the above-mentioned cyclic aluminoxane (A-1-2) and / or linear aluminoxane (A-1-3).
  • an olefin polymerization catalyst obtained by contacting the complex represented by the general formula (1), the organoaluminum compound (A-1) and the boron compound (A-2).
  • the organoaluminum compound (A-1) is easy to use as the organoaluminum compound (A-1)
  • the boron compound (A-2) is a boron compound (A-2).
  • -1) or a boron compound (A-2-2) is preferred.
  • the method for producing a stereoselective polyolefin of the present invention comprises homopolymerizing an olefin having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms in the presence of the catalyst of the present invention. Or it is a method including making it copolymerize. More preferred is homopolymerization of olefins having 3 to 6 carbon atoms.
  • homopolymerization of monoolefins having 3 to 4 carbon atoms is particularly preferred, and most preferred is propylene, This is a homopolymerization of 1-butene and 1,5-hexadiene.
  • the type of olefin to be polymerized may be single or plural. If a single olefin is polymerized, a homopolymer is obtained, and if a plurality of olefins are polymerized, a copolymer is obtained. However, in the case of homopolymerization, 1-hexene is not used as the olefin. Examples of copolymerization include propylene and 1-butene, propylene and 1-hexene, propylene and 1-butene and 1-hexene, and combinations of 1-butene and 1-hexene.
  • the olefin used for copolymerization is not particularly limited, but is preferably an olefin that exhibits desired physical properties by stereoselective polymerization.
  • the olefin can be, for example, a monoolefin or a diolefin.
  • monoolefins include carbons such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and vinylcyclohexane.
  • 1-alkene having 3 to 10 atoms (which may be branched), cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetra Cyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5 -Methoxycarboni Norbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetra
  • diolefin examples include 1,5-hexadiene, 1,4-hexadiene, 1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5 -Methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-hexadiene, 1,3-octadiene, 1,3 -Cyclooctadiene, 1,3-cyclohexadiene, butad
  • Preferred monoolefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, vinylcyclohexane, and more preferably propylene, 1-butene.
  • Vinylcyclohexane Vinylcyclohexane.
  • the diolefin is preferably 1,5-hexadiene, 1,6-heptadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5 -Methylene-2-norbornene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene, butadiene, isoprene, more preferably 1,5-hexadiene, 1,6- Heptadiene, 1,3-cyclohexadiene, butadiene and isoprene.
  • isotactic pentad fraction [mmmm] (%) is used.
  • the isotactic pentad fraction referred to here is A.I.
  • the polymer has a structure including a cyclized polymer portion and a 1,2-insert portion.
  • the cyclized polymer portion may have four structures stereochemically (cis; iso), (cis; syndio), (trans; iso), and (trans; syndio).
  • diene ring-closed polymers are known to vary greatly in polymer properties depending on the degree of stereoregularity (cis, trans; iso, syndio) and the degree of ring-close polymerization (ring-closed polymerization, 1,2-insertion). . There are a large number of such combinations, detailed studies have not been made, and the degree of stereoselectivity of known polymers is insufficient.
  • the diene ring-closing polymers are known as applications of diene ring-closing polymers as materials.
  • the diene ring-closed polymer polymerized with a high ring-closing ratio and a high stereoregularity can be used as a liquid crystalline material that is lightweight and excellent in processability.
  • Liquid crystal polymers have a high degree of molecular chain orientation without any operations such as stretching, so that high-performance fibers such as high-strength and high-modulus fibers can be obtained. Degree of dimensional stability, creep resistance, etc.
  • diene ring-closing polymers can be used as polymer-type nucleating agents by controlling their stereoselectivity.
  • Polyolefin-based crystalline polymers typified by polypropylene have the disadvantage that the polymer crystallization rate is generally slow in heat-melt molding such as injection molding, film processing, spinning processing, flat yarn molding, and hollow molding. is there.
  • Highly stereoselective diene ring-closing polymer is a polymer type nucleating agent that is excellent in dispersibility and miscibility in crystalline polyolefin, has little bleed-out, and has little odor or taste transfer problems generated from nucleating agents. Can be used as
  • an optically active diene ring closure polymer can be obtained by using an optically active catalyst.
  • an optically active catalyst By making the diene ring-closing polymer optically active, improvement in heat resistance, improvement in liquid crystallinity, and improvement in performance as a polymer nucleating agent can be expected.
  • the polymerization method is not particularly limited.
  • aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane
  • aromatic hydrocarbons such as benzene and toluene
  • halogenated hydrocarbons such as methylene dichloride.
  • Solvent polymerization using carbon as a solvent, slurry polymerization, or the like is possible, and either continuous polymerization or batch polymerization is possible.
  • the temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight, the activity of the catalyst, and the amount used.
  • the polymerization temperature can usually be in the range of ⁇ 50 ° C. to 200 ° C., but is particularly preferably in the range of ⁇ 20 ° C. to 100 ° C.
  • the polymerization pressure is usually preferably normal pressure to 50 MPa.
  • the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but it is usually in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges.
  • a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.
  • the concentration of each compound in the solvent is not particularly limited.
  • the concentration of the zirconium complex in the solvent can be selected, for example, in the range of 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L, and the concentration of the promoter component is, for example, 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L.
  • a range can be selected.
  • the volume ratio of olefin: solvent can be selected from 100: 0 to 1: 1000.
  • these ranges are examples and are not intended to be limited to them. Even when no solvent is used, the concentration can be appropriately set with reference to the above range.
  • the Q factor (/ ⁇ ) was calculated as 26.4.
  • Molecular weight (Mw, Mn) Molecular chain length (Aw, An) ⁇ Q factor (3)
  • the [mmmm] fraction of polypropylene is 21.64 to 22.22 relative to the peak area (I (CH 3 )) attributed to 19.4 to 22.2 ppm of methyl carbon in the 13 C-NMR spectrum measured under the following conditions.
  • the peak area (I (mmmm)) attributed to methyl carbon of 02 ppm mmmm pentad was determined.
  • 1 H-NMR measurement conditions ⁇ Regularity measurement condition, poly (1,5-hexadiene)> Apparatus: DPX400 manufactured by Bruker Measuring solvent: Chloroform-d Measurement temperature: 25 ° C Measurement method: Proton coupling method Pulse width: 30 degrees Pulse repetition time: 1 second Measurement standard: Residual chloroform in deuterated chloroform Window function: Negative exponential function (6) 1,5-hexadiene ring-closed polymer stereoregularity ( ⁇ , ⁇ ) Under the conditions shown below, a 13 C-NMR spectrum of a 1,5-hexadiene polymer was measured, and according to the method described in JACS, 115, 91 (1993), the enantioface selectivity index ( ⁇ ), cis selectivity index ( ⁇ ) was determined.
  • the formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure.
  • Ether and saturated aqueous ammonium chloride solution were added to the resulting residue, and the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (developing solvent hexane-dichloromethane 1: 1) to obtain 6.74 g (yield 89%) of the title compound as colorless crystals.
  • Triethylamine 1.1 mL (7.9 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and also at room temperature for 2 hours. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 0.17 mL (1.2 mmol) was added here, and it stirred at room temperature for 2 hours. After evaporating volatile components under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 0.39 mL (2.8 mmol) was added here, and it stirred at room temperature for 2 hours. After the volatile components were distilled off from the reaction solution under reduced pressure, ethyl acetate and an aqueous ammonium chloride solution were added. The organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 24 mL (172 mmol) was added here, and it heated and refluxed for 2.5 hours.
  • the reaction solution was allowed to cool to room temperature, and the insoluble material was filtered off. After evaporating volatile components from the filtrate under reduced pressure, ethyl acetate was added to the residue, followed by washing with 1M HCl and saturated brine in this order.
  • the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 19.2 g of a mixture containing 2- (1-adamantyl) -5-methylsalicylaldehyde.
  • Triethylamine 0.70 mL (5.1 mmol) was added here, and it stirred at 0 degreeC for 1 hour, and room temperature for 1 hour. Further, 90 mg (0.50 mmol) of trans-cyclooctane-1,2-dithiol was added and stirred at room temperature for 1 hour. Volatile components were distilled off under reduced pressure, and ethyl acetate and an aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • Triethylamine 0.90 mL (6.5 mmol) was added here, and it stirred at room temperature for 22.5 hours.
  • the reaction solution was filtered, and volatile components were removed from the filtrate under reduced pressure.
  • Ethyl acetate and aqueous ammonium chloride solution were added to the obtained residue.
  • Triethylamine 0.10 mL (0.72 mmol) was added here, and it stirred for 22 hours.
  • the reaction solution was filtered, and volatile components were removed from the filtrate under reduced pressure.
  • Ethyl acetate and an aqueous ammonium chloride solution were added to the obtained residue, and the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in this order. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure.
  • Triethylamine 1.0 mL (7.2 mmol) was added here, and it stirred at room temperature for 22 hours.
  • the reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure.
  • Ethyl acetate and aqueous ammonium chloride solution were added to the obtained residue.
  • the organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • the reaction solution was poured into an aqueous sodium bicarbonate solution. After the organic layer was dried over anhydrous magnesium sulfate, the volatile component was distilled off under reduced pressure.
  • reaction solution was filtered, and volatile components were distilled off from the filtrate under reduced pressure. Ethyl acetate and aqueous ammonium chloride solution were added to the resulting residue. The organic layer was further washed with an aqueous ammonium chloride solution and saturated brine in that order, and then dried over anhydrous magnesium sulfate.
  • Example 1 The autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was lowered to 0 ° C.
  • Example 2 The same procedure as in Example 1 was performed except that the polymerization temperature was 40 ° C., the amount of d-MAO charged was 118 mg, and the monomer was 1-butene. The results are shown in Table 1.
  • Example 3 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 131 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-cumyl-2-oxoylbenzylsulfanyl)] dibenzylzirconium synthesized in Reference Example 6 (0.5 mmol / L, toluene solution) The same procedure as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) was used. The results are shown in Table 1.
  • Example 4 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 124 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3- (1,1-diphenylethyl) -2-oxoylbenzylsulfanyl)] dibenzyl synthesized in Reference Example 8 The same operation as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) of zirconium (0.5 mmol / L, toluene solution) was used. The results are shown in Table 1.
  • Example 5 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 123 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-oxoyl-3- (triphenylmethyl) benzylsulfanyl] ⁇ dibenzylzirconium (0. The same procedure as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) of 5 mmol / L, toluene solution was used. The results are shown in Table 1.
  • Example 6 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 140 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [3- (1-adamantyl) -5-methyl-2-oxoylbenzylsulfanyl] ⁇ dibenzylzirconium synthesized in Reference Example 12 (0.5 The same procedure as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) of mmol / L, toluene solution was used. The results are shown in Table 1.
  • Example 7 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 129 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [2-oxoyl-3- (trimethylsilyl) -5-methylbenzylsulfanyl] ⁇ dichlorozirconium synthesized in Reference Example 14 (0.5 mmol / L, The same procedure as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) of toluene solution was used. The results are shown in Table 1.
  • Example 8 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 122 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium ⁇ Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ synthesized in Reference Example 16 instead of The same procedure as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) of dichlorozirconium (0.5 mmol / L, toluene solution) was used. The results are shown in Table 1.
  • Example 9 The autoclave with a stirrer with an internal volume of 400 mL was vacuum-dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was lowered to 0 ° C.
  • Example 10 The polymerization temperature was set to 70 ° C., and ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium ( 0.5 mmol / L, toluene solution) was 0.20 mL (0.10 ⁇ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 mmol / L, toluene solution) The same operation as in Example 9 was performed except that the input amount was 0.13 mL (0.52 ⁇ mol). The results are shown in Table 1.
  • Example 11 The polymerization temperature was set to 80 ° C., and ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium ( 0.5 mmol / L, toluene solution) was 0.20 mL (0.10 ⁇ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 mmol / L, toluene solution) The same operation as in Example 9 was performed except that the input amount was 0.13 mL (0.52 ⁇ mol). The results are shown in Table 1.
  • Example 12 The polymerization temperature was set to 90 ° C., and ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (3,5-dimethyl-1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium ( 0.5 mmol / L, toluene solution) was 0.20 mL (0.10 ⁇ mol), triphenylcarbenium tetrakis (pentafluorophenyl) borate (4.0 mmol / L, toluene solution) The same operation as in Example 9 was performed except that the input amount was 0.13 mL (0.52 ⁇ mol). The results are shown in Table 1.
  • Example 13 The polymerization was carried out in the same manner as in Example 9 except that the polymerization temperature was 70 ° C. and the solvent was 40 mL of hexane instead of 40 mL of toluene. The results are shown in Table 1.
  • Example 14 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 118 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium ⁇ Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2-phenyl-2-butyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium synthesized in Reference Example 18 instead of (0.5 mmol / L, toluene solution) The same procedure as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) was used. The results are shown in Table 1.
  • Example 15 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 123 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methyl-1-naphthylethyl) benzylsulfanyl] ⁇ dichloro synthesized in Reference Example 20 The same operation as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) of zirconium (0.5 mmol / L, toluene solution) was used. The results are shown in Table 1.
  • Example 17 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 144 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [5-tert-butyl-2-hydroxy-3- (1-methylcyclohexyl) benzylsulfanyl] ⁇ dichlorozirconium (0. 5 mmol / L, toluene solution) The same procedure as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) was used. The results are shown in Table 1.
  • Example 18 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 119 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium ⁇ Cyclooctanediyl-trans-1,2-bis [5-tert-butyl-3- (2,3-dimethyl-2-butyl) -2-hydroxybenzylsulfanyl] ⁇ synthesized in Reference Example 24 instead of The same procedure as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) of dichlorozirconium (0.5 mmol / L, toluene solution) was used. The results are shown in Table 1.
  • Example 19 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 112 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of ⁇ cyclooctanediyl-trans-1,2-bis [5-bromo-3- (1-adamantyl) -2-hydroxybenzylsulfanyl] ⁇ dichlorozirconium synthesized in Reference Example 26 (0.5 mmol / L, toluene solution) The same procedure as in Example 1 was performed except that 0.10 mL (0.050 ⁇ mol) was used. The results are shown in Table 1.
  • Example 20 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 111 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of [cyclooctanediyl-trans-1,2-bis (3-tert-amyl-5-tert-butyl-2-hydroxybenzylsulfanyl)] dichlorozirconium synthesized in Reference Example 28 (0.1 mmol / L, toluene solution) The same procedure as in Example 1 was performed except that 1.0 mL (0.10 ⁇ mol) was used. The results are shown in Table 1.
  • Example 21 The polymerization temperature was 40 ° C., the amount of d-MAO charged was 115 mg, and [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylzirconium Instead of [cyclooctanediyl-trans-1,2-bis (5-tert-butyl-3-triisopropylsilyl-2-hydroxybenzylsulfanyl)] dibenzylzirconium (0.50 mmol) synthesized in Reference Example 30 / L, toluene solution) The same procedure as in Example 1 was performed except that 1.0 mL (0.50 ⁇ mol) was used. The results are shown in Table 1.
  • Example 22 In a 50 mL Schlenk tube, 29 mg of d-MAO was dissolved in 18 mL of toluene, and 3.0 g (36.5 mmol) of 1,5-hexadiene was added to this solution. To this solution was added 2 mL of a toluene solution of 1.55 mg (0.0020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium at 25 ° C. The mixture was further stirred for 10 minutes.
  • Example 23 In a 50 mL Schlenk tube, 29 mg of d-MAO was dissolved in 18 mL of toluene, and 3.0 g (36.5 mmol) of 1,5-hexadiene was added to this solution. To this solution was added 2 mL of a toluene solution of 1.55 mg (0.0020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium at 40 ° C. The mixture was further stirred for 10 minutes.
  • Example 24 In a 50 mL Schlenk tube, 29 mg of d-MAO was dissolved in 18 mL of toluene, and 3.0 g (36.5 mmol) of 1,5-hexadiene was added to this solution. To this solution was added 2 mL of a toluene solution of 1.55 mg (0.0020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dichlorozirconium at 70 ° C. In addition, the mixture was further stirred for 10 minutes.
  • the present invention is useful in the field relating to the production of polyolefins.

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Abstract

La présente invention concerne un catalyseur de polymérisation d'oléfines permettant de produire des polymères, avec une excellente stéréorégularité, par polymérisation d'oléfines en C3-10 (à l'exception du 1-hexène), ainsi qu'un procédé de production de polymères oléfiniques au moyen dudit catalyseur de polymérisation d'oléfines. L'invention concerne un catalyseur de polymérisation d'oléfines en C3-10 (à l'exception d'un catalyseur d'homopolymérisation de 1-hexène) qui contient un complexe représenté par la formule générale (1); ainsi qu'un procédé de production d'un homopolymère oléfinique (à l'exception d'un homopolymère de 1-hexène) ou d'un copolymère oléfinique, lequel procédé met en oeuvre ledit catalyseur de polymérisation pour l'homopolymérisation ou la copolymérisation d'oléfines.
PCT/JP2012/053729 2011-02-18 2012-02-16 Catalyseur de polymérisation d'oléfines et procédé de production de polymère oléfinique WO2012111778A1 (fr)

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Publication number Priority date Publication date Assignee Title
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

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WO2011099584A1 (fr) * 2010-02-12 2011-08-18 国立大学法人埼玉大学 Catalyseur de polymérisation d'éthylène et procédé de production de polymère d'éthylène

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011099584A1 (fr) * 2010-02-12 2011-08-18 国立大学法人埼玉大学 Catalyseur de polymérisation d'éthylène et procédé de production de polymère d'éthylène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.AM.CHEM.SOC., vol. 131, no. 38, 2009, pages 13566 - 13567 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10358397B2 (en) 2017-06-29 2019-07-23 Exxonmobil Chemical Patents Inc. Production of olefin dimers

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