US20120184693A1 - Ethylene polymer preparation method - Google Patents

Ethylene polymer preparation method Download PDF

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US20120184693A1
US20120184693A1 US13/498,214 US201013498214A US2012184693A1 US 20120184693 A1 US20120184693 A1 US 20120184693A1 US 201013498214 A US201013498214 A US 201013498214A US 2012184693 A1 US2012184693 A1 US 2012184693A1
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carbon atoms
halogen atom
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Yasutoyo Kawashima
Takahiro Hino
Taichi Senda
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
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    • C07—ORGANIC CHEMISTRY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/28—Titanium compounds
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for producing an ethylenic polymer.
  • Ethylenic polymers having an alkyl side chain such as linear low-density polyethylene and ultralow-density polyethylene, have a lower melting point than that of alkyl side chain-free ethylenic polymers (e.g., high-density polyethylene) and are therefore excellent in thermal adhesiveness.
  • alkyl side chain-free ethylenic polymers e.g., high-density polyethylene
  • these polymers are used in package films for foods or pharmaceuticals, heat-sealable lidstock materials, materials for hot-melt adhesives or the like.
  • Such ethylenic polymers having an alkyl side chain have been produced so far by copolymerizing ethylene with ⁇ -olefin (e.g., 1-butene or 1-hexene) in the presence of an olefin polymerization catalyst.
  • ⁇ -olefin e.g., 1-butene or 1-hexene
  • NON-PATENT DOCUMENTS 1 and 2 have proposed a process for producing an ethylenic polymer having a lowered melting point, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride as a catalytic component for olefin polymerization, [1-dimethylphenylmethyl-cyclopentadienyl]titanium trichloride as a catalytic component for trimerization and methylaluminoxane as an activating co-catalytic component into contact with each other.
  • an olefin polymerization catalyst obtainable by bringing dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride as a catalytic component for olefin polymerization, [1-
  • an object of the present invention is to provide a process for producing an ethylenic polymer having a low melting point more economically.
  • the present invention relates to a process for producing an ethylenic polymer having a low melting point more economically, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein a particular transition metal complex is used as the catalytic component for olefin polymerization or wherein a particular transition metal complex is used as the catalytic component for trimerization.
  • a first aspect of the present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene
  • an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein the catalytic component for olefin polymerization comprises a transition metal complex represented by the following general formula (1):
  • M 1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • a 1 represents an atom of Group 16 of the Periodic Table of the Elements
  • J 1 represents an atom of Group 14 of the Periodic Table of the Elements
  • Cp 1 represents a group having a cyclopentadiene-type anionic skeleton
  • X 1 , X 2 , R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having
  • Cp 2 represents a group having a cyclopentadiene-type anionic skeleton
  • M 2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • J 2 represents a carbon atom
  • Ar represents an aryl group which may have a substituent
  • R 9 represents a hydrocarbyl group which may have a substituent or a hydrogen atom, and the two R 9 groups may be the same as or different from each other and may be bonded to each other to form ring together with J 2
  • X 3 , X 4 and X 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy
  • a second aspect of the present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene
  • an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein the catalytic component for trimerization comprises a transition metal complex represented by general formula (3):
  • M 3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • R 10 , R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, a substituted silyl group represented by —Si(R 7
  • the present invention can provide a process for economically producing an ethylenic polymer having a butyl branch and having a lowered melting point even under temperature conditions suitable for industrial production at high temperatures.
  • the term “polymerization” encompasses not only homopolymerization but also copolymerization.
  • the term “substituent” encompasses a halogen atom constituting a compound or a group.
  • the catalytic component for olefin polymerization used in the present invention is a transition metal complex represented by general formula (1):
  • M 1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • a 1 represents an atom of Group 16 of the Periodic Table of the Elements
  • J 1 represents an atom of Group 14 of the Periodic Table of the Elements
  • Cp 1 represents a group having a cyclopentadiene-type anionic skeleton
  • X 1 , X 2 , R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having
  • Examples of the transition metal atom of Group 4 of the Periodic Table of the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised, 1989) in M 1 include titanium, zirconium and hafnium atoms. A titanium atom is preferable.
  • Examples of the atom of Group 16 of the Periodic Table of the Elements in A 1 include oxygen, sulfur and selenium atoms. An oxygen atom is preferable.
  • Examples of the atom of Group 14 of the Periodic Table of the Elements represented by J 1 include carbon, silicon and germanium atoms. Carbon and silicon atoms are preferable, and a carbon atom is more preferable.
  • Examples of the group having a cyclopentadiene-type anionic skeleton represented by the substituent Cp 1 include ⁇ 5 -cyclopentadienyl, ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -dimethylcyclopentadienyl, ⁇ 5 -trimethylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -ethylcyclopentadienyl, ⁇ 5 -n-propylcyclopentadienyl, ⁇ 5 -isopropylcyclopentadienyl, ⁇ 5 -n-butylcyclopentadienyl, ⁇ 5 -sec-butylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -n-pentylcyclopentadienyl, ⁇ 5 -neopenty
  • ⁇ 5 -cyclopentadienyl, ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -indenyl and ⁇ 5 -fluorenyl, etc. are preferable.
  • halogen atoms in X 1 , X 2 , R 1 , R 2 , R 3 and R 4 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.
  • the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluoro
  • Examples of the aryl group having 6 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphen
  • the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • Examples of the aralkyl group having 7 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl
  • the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyl group listed above with a halogen atom.
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.
  • the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the alkoxy group having 1 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the alkoxy group listed above with a halogen atom.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include aryloxy groups having 6 to 20 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphen
  • the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aryloxy group having 6 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aryloxy group listed above with a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy,
  • the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aralkyloxy group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyloxy group listed above with a halogen atom.
  • the R 7 s are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-
  • a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl,
  • the total number of the carbon atoms in these three R 7 groups is preferably in the range of 3 to 18.
  • Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl
  • trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of a hydrogen atoms in these groups with a halogen atom are more preferable.
  • the two R 8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is 2 to 20, in X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , the R 8 each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10.
  • hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as a hydrocarbyl group and a halogenated hydrocarbyl group for the substituted silyl group. Moreover, these two R 8 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R 8 groups are bonded.
  • disubstituted amino group examples include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom.
  • two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, and R 5 and R 6 may be bonded to each other to form a ring together with J 1 to which R 5 and R 6 are bonded.
  • Examples of the ring include saturated or unsaturated hydrocarbyl rings and can specifically include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings. These rings may be substituted with a hydrocarbyl group having 1 to 20 carbon atoms, or the like.
  • the substituents X 1 and X 2 are preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, more preferably a halogen atom.
  • R 1 is preferably an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or a substituted silyl group represented by —Si(R 7 ) 3 (three R's each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in three R 7 s is 1 to 20).
  • the transition metal complex represented by the general formula (1) can be produced, for example, by a process described in JP 9-87313 A.
  • Examples of the complex represented by the general formula (1) include: transition metal complexes represented by the general formula (1) wherein J 1 is a carbon atom, such as methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride
  • transition metal complexes represented by the general formula (1) wherein J 1 is an atom of Group 14 of the Periodic Table of the Elements other than a carbon atom, such as dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(n-butyl cyclopentadienyl)(2-phenoxy)titanium dichloride dimethylsilylene(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butyl
  • dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride dimethylsilylene(indenyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride,
  • the catalytic component for trimerization used in the first aspect of the present invention is a transition metal complex represented by the following general formula (2):
  • Cp 1 represents a group having a cyclopentadiene-type anionic skeleton
  • M 2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • J 2 represents a carbon atom
  • Ar represents an aryl group which may have a substituent
  • R 9 represents a hydrocarbyl group which may have a substituent or a hydrogen atom, and the two R 9 groups may be the same as or different from each other and may be bonded to each other to form ring together with J 2
  • X 3 , X 4 and X 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy
  • the group having a cyclopentadiene-type anionic skeleton represented by the substituent Cp 1 is a ⁇ 5 -cyclopentadienyl group or a cyclopentadienyl group having at least one substituent.
  • Examples of the cyclopentadienyl group having at least one substituent include ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -dimethylcyclopentadienyl, ⁇ 5 -trimethylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -ethylcyclopentadienyl, ⁇ 5 -n-propylcyclopentadienyl, ⁇ 5 -isopropylcyclopentadienyl, ⁇ 5 -n-butylcyclopentadienyl, ⁇ 5 -sec-butylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -n-pentylcyclopentadienyl, ⁇ 5 -neopentylcyclopentadienyl, ⁇ 5 -n-hexylcyclopent
  • the cyclopentadienyl group having at least one substituent is preferably ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -ethylcyclopentadienyl, ⁇ 5 -n-propylcyclopentadienyl, ⁇ 5 -isopropylcyclopentadienyl, ⁇ 5 -n-butylcyclopentadienyl, ⁇ 5 -sec-butylcyclopentadienyl, ⁇ 5 -ten-butylcyclopentadienyl, ⁇ 5 -dimethylcyclopentadienyl, ⁇ 5 -trimethylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -indenyl or ⁇ 5 -trimethylsilylcyclopentadienyl group, etc., more preferably ⁇ 5 -methylcyclopentadienyl, ⁇ 5
  • J 2 is a carbon atom.
  • aryl group which may have a substituent represented by Ar examples include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n
  • halogen atom examples include fluorine, chlorine, bromine and iodine atoms.
  • the aryl group is preferably a phenyl group or a phenyl group having an alkyl group having 1 to 4 carbon atoms as a substituent, specifically, a 3,5-dimethylphenyl, tetramethylphenyl, n-butylphenyl, sec-butylphenyl or tert-butylphenyl group, etc.
  • Examples of the transition metal atom of Group 4 of the Periodic Table of the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised, 1989) in M 2 include titanium, zirconium and hafnium atoms. Titanium and zirconium atoms are preferable, and a titanium atom is more preferable.
  • the two R 9 groups may be bonded to each other to form a ring together with the carbon atoms to which the two R 9 groups are bonded.
  • specific examples of the ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, benzene, naphthalene and anthracene rings.
  • halogen atom in X 3 , X 4 and X 5 examples include fluorine, chlorine, bromine and iodine atoms. A chlorine atom is preferable.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X 3 , X 4 and X 5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.
  • the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluoro
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X 3 , X 4 and X 5 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.
  • the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the alkoxy group having 1 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the alkoxy group listed above with a halogen atom.
  • Examples of the aryl group having 6 to 20 carbon atoms in X 3 , X 4 and X 5 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pent
  • the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X 3 , X 4 and X 5 include aryloxy groups having 6 to 20 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy,
  • the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aryloxy group having 6 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aryloxy group listed above with a halogen atom.
  • Examples of the aralkyl group having 7 to 20 carbon atoms in X 3 , X 4 and X 5 include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (p
  • the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyl group listed above with a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X 3 , X 4 and X 5 include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-
  • the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with a halogen atom.
  • the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • the aralkyloxy group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyloxy group listed above with a halogen atom.
  • the R 7 s are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g.,
  • the total number of the carbon atoms in these three R 7 groups is preferably in the range of 3 to 18.
  • Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethyls
  • trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are more preferable.
  • the R 8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is 2 to 20, in X 3 , X 4 and X 5 , the R 8 s each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10.
  • hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as a hydrocarbyl group and a halogenated hydrocarbyl group for the substituted silyl group. Moreover, these two R 8 groups may be bonded to each other to form a ring together with the nitrogen atom bonded thereto.
  • disubstituted amino group examples include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom.
  • transition metal complex represented by the general formula (2) examples include (1-phenylmethyl-cyclopentadienyl)titanium trichloride, (1-diphenylmethyl-cyclopentadienyl)titanium trichloride, (1-triphenylmethyl-cyclopentadienyl)titanium trichloride, [1-(2-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(4-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,4-dimethylphenyl)methyl-cyclopentadienyl]titanium trichlor
  • the transition metal complex represented by the general formula (2) can be produced, for example, by a process described in Organometallics 2002, 21, pp 5122-5135.
  • the catalytic component for trimerization used in the second aspect of the present invention is a transition metal complex represented by the following general formula (3):
  • M 3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • R 10 , R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, a substituted silyl group represented by —Si(R 7
  • M 3 represents an element of Group 4 of the Periodic Table of the Elements, and examples thereof include titanium, zirconium and hafnium atoms. Among them, a titanium atom is preferable.
  • the substituents R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , X 6 , X 7 and X 8 are as defined above, and specific examples thereof are shown below.
  • the halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.
  • the preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof can include methyl, ethyl, isopropyl, tert-butyl and amyl groups.
  • the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.
  • the alkyl group having a halogen atom as a substituent can include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexyl groups.
  • the preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof include a phenyl group.
  • the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • aryl group having a halogen atom as a substituent specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • the preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof include a benzyl group.
  • the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aralkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • the preferable alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and more preferable examples thereof can include methoxy, ethoxy and tert-butoxy groups.
  • the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.
  • the preferable aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and more preferable examples thereof can include phenoxy, 2-methylphenoxy, 3-methylphenoxy and 4-methylphenoxy groups.
  • the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • the preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyloxy group.
  • the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aralkyloxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • the R 7 groups are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); or a halogenated hydrocar
  • the total number of the carbon atoms in these three R 7 groups is preferably in the range of 3 to 18.
  • Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl
  • trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are more preferable.
  • the R 8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is 2 to 20, the R 8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10.
  • the hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as the hydrocarbyl group and the halogenated hydrocarbyl group for the substituted silyl group.
  • these two R 8 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R 8 groups are bonded.
  • Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups
  • R 15 and R 16 may be bonded to each other to form a ring together with the silicon atom to which R 15 and R 16 are bonded, and of R 10 , R 11 , R 12 , R 13 and R 14 , two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which the two groups are bonded.
  • the ring can be a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, or the like.
  • cyclopropane examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings.
  • R 10 , R 11 , R 12 , R 13 and R 14 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.
  • Examples of a preferable combination of R 10 , R 11 , R 12 , R 13 and R 14 can include those that can provide the following substructures represented by a substructural formula (4):
  • R 10 , R 11 , R 12 , R 13 and R 14 are as defined above:
  • phenyl methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl and bis(trifluoromethyl)phenyl.
  • the preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, pentamethylphenyl or the like.
  • R 15 and R 16 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, naphthyl and benzyl group.
  • Examples of a preferable combination of R 15 and R 16 can include those that can provide the following substructures represented by a substructural formula (5):
  • R 15 and R 16 are as defined above:
  • the preferable silylene substructure is dimethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclotetramethylenesilylene, or the like.
  • transition metal complex (3) can include the following complexes:
  • the transition metal complex represented by the general formula (3) can be produced, for example, by process described in J. Organomet. Chem. 1999, 592, pp 84-94.
  • Examples of the activating co-catalytic component can include compounds (A) and (B) shown below. These compounds (A) and (B) may be used in combination:
  • Compound (A) one or more aluminum compounds selected from the compound group consisting of the following compounds (A1) to (A3):
  • (A1) an organic aluminum compound represented by a general formula (E 1 ) a Al(G) 3-a ,
  • (A2) a cyclic aluminoxane having a structure represented by a general formula ⁇ —Al(E 2 )—O— ⁇ b , and
  • (A3) a linear aluminoxane having a structure represented by a general formula E 3 ⁇ —Al(E 3 )—O— ⁇ c Al(E 3 ) 2 , wherein
  • E 1 , E 2 and E 3 represent a hydrocarbyl group having 1 to 8 carbon atoms;
  • G represents a hydrogen atom or a halogen atom;
  • a represents an integer of 1 to 3;
  • b represents an integer of 2 or more;
  • c represents an integer of 1 or more;
  • E 1 groups may be the same or different from each other when more than one E 1 groups exist;
  • G groups may be the same or different from each other when one or more G groups exist;
  • E 2 groups may be the same or different from each other; and
  • E 3 groups may be the same or different from each other.
  • Compound (B) one or more boron compounds selected from the compound group consisting of the following compounds (B1) to (B3):
  • (B1) a boron compound represented by a general formula BQ 1 Q 2 Q 3 ,
  • (B2) a borate compound represented by a general formula T + (BQ 1 Q 2 Q 3 Q 4 ) ⁇ , and
  • B represents a trivalent boron atom
  • Q 1 , Q 2 , Q 3 and Q 4 are the same as or different from each other and each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a hydrocarbylsilyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a dihydrocarbylamino group having 2 to 20 carbon atoms;
  • T + represents an inorganic or organic cation; and (L-H) + represents a Broensted acid.
  • examples of the hydrocarbyl group having 1 to 8 carbon atoms in E 1 , E 2 and E 3 include alkyl having 1 to 8 carbon atoms.
  • examples of the alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl group.
  • Examples of the organic aluminum compound (A1) represented by the general formula (E 1 ) a Al(G) 3-a include trialkylaluminums, dialkylaluminum chlorides, alkylaluminum dichlorides and dialkylaluminum hydrides.
  • Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum.
  • Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride.
  • alkylaluminum dichloride examples include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride.
  • dialkylaluminum hydride examples include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
  • aluminoxanes are prepared by various methods.
  • the methods are not particularly limited, and they may be prepared according to methods known in the art.
  • a solution containing a trialkylaluminum (e.g., trimethylaluminum) dissolved in an appropriate organic solvent (e.g., benzene or aliphatic hydrocarbyl) is contacted with water to prepare the aluminoxanes.
  • Another preparation method can involve, for example, contacting a trialkylaluminum (e.g., trimethylaluminum) with a metal salt (e.g., copper sulfate hydrate) containing crystalline water.
  • a metal salt e.g., copper sulfate hydrate
  • Al(E 3 ) 2 include alkyl groups such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl groups.
  • b is an integer of 2 or more
  • c is an integer of 1 or more.
  • E 2 and E 3 are each independently a methyl group or an isobutyl group
  • b is 2 to 40
  • C is 1 to 40.
  • Q 1 , Q 2 , Q 3 and Q 4 are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom.
  • examples of the inorganic cation in T + include ferrocenium cation, alkyl-substituted ferrocenium cations and silver cation.
  • examples of the organic cation in T + include triphenylmethyl cation.
  • Examples of (BQ 1 Q 2 Q 3 Q 4 ) ⁇ include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate and tetrakis(3,5-bistrifluoromethylphenyl)borate.
  • Examples of the Broensted acid represented by (L-H) + include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium and triarylphosphonium.
  • Examples of the boron compound (B1) represented by the general formula BQ 1 Q 2 Q 3 include 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 and phenylbis(pentafluorophenyl)borane.
  • borate compound (B2) represented by the general formula T + (BQ 1 Q 2 Q 3 Q 4 ) ⁇ examples include ferrocenium tetrakis(pentafluorophenyl)borate, 1,1′-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate.
  • borate compound (B3) represented by the general formula (L-H) + (BQ 1 Q 2 Q 3 Q 4 ) ⁇ include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N,
  • the olefin polymerization catalyst used in the first aspect of the present invention is a catalyst obtainable by bringing the catalytic component for olefin polymerization comprising the transition metal complex represented by the general formula (1), the catalytic component for trimerization comprising the transition metal complex represented by the general formula (2) and the activating co-catalytic component into contact with each other.
  • the olefin polymerization catalyst used in the second aspect of the present invention is a catalyst obtainable by bringing the catalytic component for olefin polymerization, the catalytic component for trimerization comprising the transition metal complex represented by the general formula (3) and the activating co-catalytic component into contact with each other.
  • the molar ratio between the catalytic component for trimerization and the catalytic component for olefin polymerization is usually 0.0001 to 100, preferably 0.001 to 1, more preferably 0.01 to 0.5, even more preferably 0.05 to 0.15.
  • the molar ratio between the compound (A) (in terms of the aluminum atom) and the transition metal complexes used as catalytic components (total of the catalytic component for trimerization and the catalytic component for olefin polymerization) (compound (A) (in terms of the aluminum atom)/transition metal complexes) is usually 0.01 to 10000, preferably 5 to 2000.
  • the molar ratio between the compound (B) and the transition metal complexes used as catalytic components is usually 0.01 to 100, preferably 0.5 to 10.
  • the concentration of the transition metal complex used as a catalytic component is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • the concentration of the compound (A) is usually 0.01 to 500 mmol/L, preferably 0.1 to 100 mmol/L, in terms of the aluminum atom.
  • the concentration of the compound (B) is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • Each catalytic component may be supported by a carrier for use.
  • a porous substance is preferably used as a carrier. More preferably an inorganic substance or an organic polymer, even more preferably an inorganic substance, is used.
  • the carrier will be described later.
  • the method for bringing each catalytic component into contact with each other is not particularly limited.
  • the catalytic component for olefin polymerization, the catalytic component for trimerization and the activating co-catalytic component may be brought into contact with each other in advance to prepare a polymerization catalyst, which is then supplied to a polymerization reactor.
  • these catalytic components may be supplied to a polymerization reactor in any order and subjected to contact treatment in the polymerization reactor.
  • the catalytic component for olefin polymerization brought into contact with the catalytic component for trimerization in advance may also be supplied to a polymerization reactor.
  • the catalytic component for olefin polymerization brought into contact with the activating co-catalytic component in advance may be supplied thereto.
  • the catalytic component for trimerization brought into contact with the activating co-catalytic component in advance may be supplied thereto.
  • examples of the inorganic substance used as a carrier include inorganic oxides and magnesium compounds. Clay, clay mineral, or the like may also be used. They may be mixed for use.
  • the inorganic oxides used as a carrier can include SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 and mixtures thereof, for example, SiO 2 —MgO, SiO 2 —Al 2 O 3 , SiO 2 —TiO 2 , SiO 2 —V 2 O 5 , SiO 2 —Cr 2 O 3 and SiO 2 —TiO 2 —MgO.
  • SiO 2 and Al 2 O 3 are preferable, and SiO 2 is more preferable.
  • These inorganic oxides may contain a small amount of a carbonate, sulfate, nitrate or oxide component such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O, and Li 2 O.
  • a carbonate, sulfate, nitrate or oxide component such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O, and Li 2 O.
  • the inorganic oxides usually have a hydroxy group formed on its surface.
  • Modified inorganic oxides obtained by substituting active hydrogen in the surface hydroxy group with various substituents may be used as the inorganic oxides, and a preferable substituent is a silyl group.
  • modified inorganic oxides include inorganic oxides treated by contact with a trialkylchlorosilane such as trimethylchlorosilane and tertbutyldimethylchlorosilane, a triarylchlorosilane such as triphenylchlorosilane, a dialkyldichlorosilane such as dimethyldichlorosilane, a diaryldichlorosilane such as diphenyldichlorosilane, an alkyltrichlorosilane such as methyltrichlorosilane, an aryltrichlorosilane such as phenyltrichlorosilane, a trialkylalkoxysilane such as trimethylmethoxysilane, a triarylalkoxysilane such as triphenylmethoxysilane, a dialkyldialkoxysilane such as dimethyldimethoxysilane, a diaryldialkoxy
  • Examples of the magnesium compounds used as a carrier can include: a magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; an alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride; an aryloxy magnesium halide such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; an alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; an aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and a carboxylate of magnesium such as magnesium laurate and magnesium stearate.
  • a magnesium halide or an alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.
  • Examples of the clay or clay mineral used as a carrier include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc, micas isinglass, montmorillonites, vermiculite, chlorites, palygorskite, kaolinite, nacrite, dickite halloysite, and son on.
  • smectite, a montmorillonite, hectorite, Laponite or saponite is preferable, and a montmorillonite or hectorite is more preferable.
  • the inorganic substance used as a carrier is preferably inorganic oxide.
  • the temperature of the heat treatment is usually 100 to 1500° C., preferably 100 to 1000° C., more preferably 200 to 800° C.
  • the time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the method for the heat treatment include, but not limited to, a method in which after heating, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • dried inert gas e.g., nitrogen or argon
  • the average particle size of the carrier comprising the inorganic substance is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, even more preferably 10 to 100 p.m.
  • the pore volume of the carrier comprising the inorganic substance is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g.
  • the specific surface of the carrier comprising the inorganic substance is preferably 10 to 1000 m 2 /g, more preferably 100 to 500 m 2 /g.
  • the organic polymer used as a carrier is not particularly limited, and two or more organic polymers may be used as a mixture.
  • a polymer having a group having active hydrogen and/or a non-proton-donating Lewis-basic group is preferable.
  • the group having active hydrogen is not particularly limited as long as it has active hydrogen.
  • Specific examples thereof include primary amino, secondary amino, imino, amide, hydrazide, amidino, hydroxy, hydroperoxy, carboxyl, formyl, carbamoyl, sulfonic acid, sulfinic acid, sulfenic acid, thiol, thioformyl, pyrrolyl, imidazolyl, piperidyl, indazolyl and carbazolyl groups.
  • a primary amino, secondary amino, imino, amide, imide, hydroxy, formyl, carboxyl, sulfonic acid or thiol group is preferable.
  • a primary amino, secondary amino, amide or hydroxy group is particularly preferable. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • the non-proton-donating Lewis-basic group is not particularly limited as long as it is a group having a Lewis base moiety free from an active hydrogen atom.
  • Specific examples thereof include pyridyl, N-substituted imidazolyl, N-substituted indazolyl, nitrile, azide, N-substituted imino, N,N-substituted amino, N,N-substituted aminooxy, N,N,N-substituted hydrazino, nitroso, nitro, nitrooxy, furyl, carbonyl, thiocarbonyl, alkoxy, alkyloxycarbonyl, N,N-substituted carbamoyl, thioalkoxy, substituted sulfinyl, substituted sulfonyl and substituted sulfonic acid groups.
  • Heterocyclic groups are preferable, and aromatic heterocyclic groups having oxygen and/or nitrogen atoms in the ring are more preferable.
  • a pyridyl, N-substituted imidazolyl or N-substituted indazolyl group is particularly preferable, with a pyridyl group most preferred.
  • These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • the amount of the group having active hydrogen and the non-proton-donating Lewis-basic group in the polymer is preferably 0.01 to 50 mmol/g, more preferably 0.1 to 20 mmol/g, in terms of the molar amount of the group per unit gram of the polymer.
  • the polymer having such group(s) can be obtained, for example, by homopolymerizing monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups or by copolymerizing such a monomer with additional monomer(s) having one or more polymerizable unsaturated groups.
  • a polymerizable crosslinking monomer having two or more polymerizable unsaturated groups is preferably used as at least one of the additional monomers.
  • Examples of such monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups can include monomers having the group having active hydrogen and one or more polymerizable unsaturated groups, and monomers having the group having a Lewis base moiety free from an active hydrogen atom and one or more polymerizable unsaturated groups.
  • Examples of such polymerizable unsaturated groups include: alkenyl groups such as vinyl and allyl; and alkynyl groups such as an ethyne group.
  • Examples of the monomers having the group having active hydrogen and one or more polymerizable unsaturated groups can include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds and vinyl group-containing hydroxy compounds. Specific examples thereof include N-(1-ethenyl)amine, N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine, N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide, N-methyl-(1-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol, 2-propen-1-ol and 3-buten-1-ol.
  • monomers having the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups can include vinylpyridine, vinyl (N-substituted) imidazole and vinyl (N-substituted) indazole.
  • additional monomers having one or more polymerizable unsaturated groups include olefin and aromatic vinyl compounds and specifically include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and styrene. Ethylene or styrene is preferable. These monomers may be used in combination of two or more thereof. Moreover, specific examples of the polymerizable crosslinking monomer having two or more polymerizable unsaturated groups include divinylbenzene.
  • the average particle size of the carrier comprising the organic polymer is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m.
  • the pore volume of the carrier comprising the organic polymer is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g.
  • the specific surface of the carrier comprising the organic polymer is preferably 10 to 1000 m 2 /g, more preferably 50 to 500 m 2 /g.
  • These organic polymers used as a carrier are preferably dried, for use, by heat treatment.
  • the temperature of the heat treatment is usually 30 to 400° C., preferably 50 to 200° C., more preferably 70 to 150° C.
  • the time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the method for the heat treatment include, but not limited to, a method in which after heating, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • dried inert gas e.g., nitrogen or argon
  • the geometric standard deviation of the particle size of the carrier based on the volume is preferably 2.5 or lower, more preferably 2.0 or lower, even more preferably 1.7 or lower.
  • the present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene in the presence of the olefin polymerization catalyst.
  • the polymerization may be performed by supplying only ethylene as a raw material monomer or by supplying an ethylene-copolymerizable monomer and ethylene.
  • Examples of the ethylene-copolymerizable monomer include: olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 4-methyl-1-hexene; cyclic olefins such as norbornene; alkenyl aromatic hydrocarbyl compounds such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate; and vinyl ester compounds such as vinyl acetate. These monomers may be used alone or in combination of two or more thereof.
  • olefins having 3 to 20 carbon atoms such as propylene,
  • the polymerization process is not particularly limited and can be, for example, solvent polymerization or slurry polymerization using aliphatic hydrocarbyl (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbyl (benzene, toluene, etc.) or hydrocarbyl halide (methylene dichloride, etc.) as a solvent, or gas-phase polymerization carried out in monomers in gas phase, or the like. Moreover, both continuous polymerization and batch polymerization can be carried out.
  • aliphatic hydrocarbyl butane, pentane, hexane, heptane, octane, etc.
  • aromatic hydrocarbyl benzene, toluene, etc.
  • hydrocarbyl halide methylene dichloride, etc.
  • the present invention can produce a polymer having a butyl branch and having a lowered melting point even by polymerization using hexene supplied in small amounts as a raw material monomer or by polymerization using only ethylene supplied as a raw material monomer. Therefore, polymerization conditions that make the advantages of the present invention more significant involve an ethylene molar fraction (the total amount of ethylene and 1-hexene in the polymerization system is defined as 100 mol %) of preferably 90 mol % or larger, more preferably 95 mol % or larger, even more preferably, substantially 100 mol %, in the polymerization system, when the polymerization form is slurry polymerization.
  • the ethylene molar fraction (the total amount of ethylene and 1-hexene in the polymerization system is defined as 100 mol %) is preferably 97 mol % or larger, more preferably 98 mol % or larger, even more preferably, substantially 100 mol %, in the polymerization system.
  • the concentration of the olefin polymerization catalyst in the polymerization solution is usually 0.0001 to 5 mmol/L in terms of the mole of the transition metal complexes used as catalytic components (total of the catalytic component for trimerization and the catalytic component for olefin polymerization).
  • the concentration of the olefin polymerization catalyst is preferably 2 mmol/L or lower, more preferably 1 mmol/L or lower, to improve the economical efficiency.
  • the concentration of the olefin polymerization catalyst is preferably 0.001 mmol/L or higher, more preferably 0.01 mmol/L or higher, even more preferably 0.1 mmol/L or higher, particularly preferably 0.5 mmol/L or higher, for lowering the melting point and further increasing the butyl branches.
  • the polymerization pressure is preferably from the normal pressure to 5 MPa.
  • the polymerization time is generally determined according to the type of the polymer of interest and a reaction apparatus as appropriate, and can be in the range of 1 minute to 20 hours.
  • a chain transfer agent such as hydrogen can also be added for controlling the molecular weight of the ethylenic polymer.
  • the polymerization temperature can be in the range of 0° C. to 220° C.
  • the polymerization temperature is preferably 20° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, most preferably 70° C. or higher, to improve the economic efficiency.
  • the polymerization temperature is preferably 130° C. or lower, more preferably 100° C. or lower, for lowering the melting point and further increasing the butyl branches.
  • Examples of the ethylenic polymer obtained by the production process of the present invention include ethylene-1-hexene, ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene, ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene, ethylene-1-hexene-1-butene-1-octene, ethylene-1-hexene-1-butene-4-methyl-1-pentene, ethylene-1-hexene-styrene, ethylene-1-hexene-norbornene, ethylene-1-hexene-propylene-styrene and ethylene-1-hexene-propylene-norbornene copolymers.
  • the ethylenic polymer is preferably an ethylene-1-hexene, ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene, ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene, ethylene-1-hexene-styrene or ethylene-1-hexene-norbornene copolymer, more preferably an ethylene-1-hexene or ethylene-1-hexene-1-butene copolymer.
  • the number of butyl branches per 1000 carbon atoms in the ethylenic polymer is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 10 or more, from the viewpoint of improving the mechanical strength of the ethylenic polymer. Moreover, the number of butyl branches is preferably 40 or less, more preferably 30 or less, even more preferably 25 or less, from the viewpoint of enhancing the stiffness of the ethylenic polymer.
  • the number of butyl branches can be determined by a method such as carbon nuclear magnetic resonance ( 13 C-NMR) or IR spectroscopy.
  • the melting point of the ethylenic polymer is preferably lower than 130° C. from the viewpoint of improving the mechanical strength of the ethylenic polymer.
  • the melting point can be determined using a differential scanning calorimeter.
  • the number of butyl branches per 1000 carbon atoms in the ethylenic polymer can be increased by increasing a molar ratio between the catalytic component for trimerization and the catalytic component for olefin polymerization (catalytic component for trimerization/catalytic component for olefin polymerization) used in the preparation of the polymerization catalyst or by lowering the polymerization temperature.
  • the molecular weight distribution (Mw/Mn) of the ethylenic polymer is preferably 1.5 or higher for improving the processability of the polymer. Moreover, Mw/Mn is preferably 20 or lower for improving the mechanical strength of the polymer.
  • the molecular weight distribution (Mw/Mn) is a value (Mw/Mn) obtained by deviding the weight-average molecular weight (Mw) by the number-average molecular weight (Mn) both determined by gel permeation chromatography in terms of polystyrene standards.
  • the ethylenic polymer is molded, for use, into various types of moldings (e.g., films, sheets and containers (bottles, trays, etc.)) by a molding method known in the art, for example: extrusion methods such as inflation film molding and T-die film molding; hollow molding, injection molding; compression molding; and cross-linked foaming molding.
  • a molding method known in the art for example: extrusion methods such as inflation film molding and T-die film molding; hollow molding, injection molding; compression molding; and cross-linked foaming molding.
  • the ethylenic polymer may be blended with a resin known in the art and then molded.
  • the moldings may be a monolayer molding containing the ethylenic polymer or may be a multilayer molding comprising a layer containing the ethylenic polymer.
  • moldings include films for food package, containers for food package, packaging materials for pharmaceuticals, surface-protective films, packaging materials for electronic parts used in packages for semiconductor products or the like, cross-linked foamed moldings, injection foamed moldings, hollow moldings, blow bottles and squeeze bottles.
  • Measurement values of each item in Examples and Comparative Examples were measured according to methods shown below. If necessary, an appropriate amount (e.g., 1000 ppm) of an antioxidant was formulated to measurement samples in advance.
  • the melting point of the polymer was measured under the following conditions using a differential scanning calorimeter (DSC6200R, manufactured by Seiko Instruments Inc.). The melting point was determined from a thermogram in the second heating.
  • the number of butyl branches in the obtained polymer was determined from the infrared absorption spectra. In this context, the measurement and the calculation were performed using hexene-derived characteristic absorption according to a method described in a literature (Characterization of Polyethylene based on Infrared Absorption Spectra, Takayama, Usami, et al.). The number of butyl branches was indicated in terms of the number of branches per 1000 carbon atoms (Me/1000 C).
  • toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 ⁇ L) of methylaluminoxane (TMAO, manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave.
  • TMAO methylaluminoxane
  • a toluene solution (900 ⁇ L) of 0.01 ⁇ mol of [1-(1-methyl-1-phenylsilyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 ⁇ mol of dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 2) was supplied to the autoclave to initiate the polymerization. The polymerization was performed at 70° C. for 3 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value.
  • the ethylene in the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 47.4 ⁇ 10 6 g per 1 mol of a transition metal complex per hour.
  • toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 ⁇ L) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to in the autoclave.
  • TMAO methylaluminoxane
  • the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 49.9 ⁇ 10 6 g per 1 mol of a transition metal complex per hour.
  • toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C. and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 ⁇ L) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to in the autoclave.
  • TMAO methylaluminoxane
  • the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 33.1 ⁇ 10 6 g per 1 mol of a transition metal complex per hour.
  • the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 12.9 ⁇ 10 6 g per 1 mol of a transition metal complex per hour.
  • toluene (3.64 ml) was placed under a nitrogen atmosphere.
  • the interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system.
  • a toluene solution 160 ⁇ L of triisobutylaluminum having a concentration of 0.25 mmol/mL was supplied to the autoclave.
  • toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 ⁇ L) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave.
  • TMAO methylaluminoxane
  • the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 21.1 ⁇ 10 6 g per mol of a transition metal complex per hour.
  • toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 ⁇ L) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave.
  • TMAO methylaluminoxane
  • toluene (3.64 ml) was placed under a nitrogen atmosphere.
  • the interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system.
  • a toluene solution 160 ⁇ L of triisobutylaluminum having a concentration of 0.25 mmol/mL was supplied to the autoclave.
  • toluene (3.64 ml) was placed under a nitrogen atmosphere.
  • the interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system.
  • a toluene solution 160 ⁇ L of triisobutylaluminum having a concentration of 0.25 mmol/mL, was supplied to in the autoclave.
  • ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value.
  • the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer.
  • the activity was 63.0 ⁇ 10 6 g per mol of a transition metal complex per hour.
  • the production process of the present invention has high industrial applicability as being capable of producing an ethylenic polymer having a low melting point economically.

Abstract

Disclosed is a method for preparing an ethylenic polymer with a low melting point in a more economical manner. In the ethylenic polymer preparation method, ethylene is polymerized under the presence of an olefin polymerization catalyst that is obtained by bringing an olefin polymerization catalytic component that comprises a transition metal complex represented by the following general formula (1), a trimerization catalytic component that comprises a transition metal complex represented by the following general formula (2), and an activating co-catalytic component into contact with each other.
Figure US20120184693A1-20120719-C00001

Description

    TECHNICAL FIELD
  • The present invention relates to a process for producing an ethylenic polymer.
    • BACKGROUND ART
  • Ethylenic polymers having an alkyl side chain (e.g., an ethyl or butyl branch), such as linear low-density polyethylene and ultralow-density polyethylene, have a lower melting point than that of alkyl side chain-free ethylenic polymers (e.g., high-density polyethylene) and are therefore excellent in thermal adhesiveness. Thus, these polymers are used in package films for foods or pharmaceuticals, heat-sealable lidstock materials, materials for hot-melt adhesives or the like.
  • Such ethylenic polymers having an alkyl side chain have been produced so far by copolymerizing ethylene with α-olefin (e.g., 1-butene or 1-hexene) in the presence of an olefin polymerization catalyst.
  • However, the conventional process for producing an ethylenic polymer having an alkyl side chain requires the usage of ethylene and expensive α-olefin as raw material monomers and was thus a less-than-sufficient process economically. Thus, a process for producing an ethylenic polymer having an alkyl side chain in which only ethylene is used as a raw material monomer has been studied recently.
  • For example, NON-PATENT DOCUMENTS 1 and 2 have proposed a process for producing an ethylenic polymer having a lowered melting point, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride as a catalytic component for olefin polymerization, [1-dimethylphenylmethyl-cyclopentadienyl]titanium trichloride as a catalytic component for trimerization and methylaluminoxane as an activating co-catalytic component into contact with each other.
    • CITATION LIST Non-Patent Document
    • NON-PATENT DOCUMENT 1: Zhibin Ye, et al., “A Tandem Catalytic System for the Synthesis of Ethylene-Hex-1-ene Copolymers from Ethylene Stock”, Macromolecular Rapid Communications, (Germany), Wiley-VCH, 2004, Vol. 25, p. 647-652
    • NON-PATENT DOCUMENT 2: Fahad Alobaidi, et al., “Direct Synthesis of Linear Low-Density Polyethylene of Ethylene/1-Hexene from Ethylene with a Tandem Catalytic System in a Single Reactor”, Journal of Polymer Science, Part A: Polymer Chemistry, (US), Wiley Periodicals, Inc., 2004, Vol. 42, p. 4327-4336
    SUMMARY OF THE INVENTION Problems to be Solved by the Invention
  • However, the process described above was not always sufficient economically, for example, due to the need of a catalytic component for trimerization to be used in large amounts.
  • Under such circumstances, an object of the present invention is to provide a process for producing an ethylenic polymer having a low melting point more economically.
    • Means for Solving the Problems
  • The present invention relates to a process for producing an ethylenic polymer having a low melting point more economically, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein a particular transition metal complex is used as the catalytic component for olefin polymerization or wherein a particular transition metal complex is used as the catalytic component for trimerization.
  • Specifically, a first aspect of the present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene
  • in the presence of an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein
    the catalytic component for olefin polymerization comprises a transition metal complex represented by the following general formula (1):
  • Figure US20120184693A1-20120719-C00002
  • wherein
    M1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
    A1 represents an atom of Group 16 of the Periodic Table of the Elements;
    J1 represents an atom of Group 14 of the Periodic Table of the Elements;
    Cp1 represents a group having a cyclopentadiene-type anionic skeleton;
    X1, X2, R1, R2, R3 and R4 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    R5 and R6 each independently represent
    a hydrogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    of R1, R2, R3 and R4, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X1 and X2 may be bonded to each other to form a ring together with M1; and R5 and R6 may be bonded to each other to form a ring together with J1, and
    the catalytic component for trimerization comprises a transition metal complex represented by general formula (2):

  • [Cp2-J2(R9)2—Ar]M2X3X4X5  (2)
  • wherein Cp2 represents a group having a cyclopentadiene-type anionic skeleton; M2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements; J2 represents a carbon atom; Ar represents an aryl group which may have a substituent; R9 represents a hydrocarbyl group which may have a substituent or a hydrogen atom, and
    the two R9 groups may be the same as or different from each other and may be bonded to each other to form ring together with J2; and
    X3, X4 and X5 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, and
    of X3, X4 and X5, two groups may be bonded to each other to form a ring together with M2.
  • A second aspect of the present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene
  • in the presence of an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein
    the catalytic component for trimerization comprises a transition metal complex represented by general formula (3):
  • Figure US20120184693A1-20120719-C00003
  • wherein
    M3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
    R10, R11, R12, R13 and R14 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    R15 and R16 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    X6, X7 and X8 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    of R10, R11, R12, R13 and R14, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X6, X7 and X8 may be bonded to each other to form a ring together with M3; and R15 and R16 may be bonded to each other to form a ring together with the silicon atom to which R15 and R16 are bonded.
    • Advantages of the Invention
  • The present invention can provide a process for economically producing an ethylenic polymer having a butyl branch and having a lowered melting point even under temperature conditions suitable for industrial production at high temperatures.
    • DESCRIPTION OF EMBODIMENTS
  • In the present invention, the term “polymerization” encompasses not only homopolymerization but also copolymerization. Moreover, in the present invention, the term “substituent” encompasses a halogen atom constituting a compound or a group.
    • <Catalytic Component for Olefin Polymerization>
  • The catalytic component for olefin polymerization used in the present invention is a transition metal complex represented by general formula (1):
  • Figure US20120184693A1-20120719-C00004
  • wherein
    M1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
    A1 represents an atom of Group 16 of the Periodic Table of the Elements;
    J1 represents an atom of Group 14 of the Periodic Table of the Elements;
    Cp1 represents a group having a cyclopentadiene-type anionic skeleton;
    X1, X2, R1, R2, R3 and R4 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    R5 and R6 each independently represent
    a hydrogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    of R1, R2, R3 and R4, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, X1 and X2 may be bonded to each other to form a ring together with M′ to which X1 and X2 are bonded; and R5 and R6 may be bonded to each other to form a ring together with J1 to which R5 and R6 are bonded.
  • The complex represented by the general formula (1) will be described in detail. Examples of the transition metal atom of Group 4 of the Periodic Table of the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised, 1989) in M1 include titanium, zirconium and hafnium atoms. A titanium atom is preferable.
  • Examples of the atom of Group 16 of the Periodic Table of the Elements in A1 include oxygen, sulfur and selenium atoms. An oxygen atom is preferable.
  • Examples of the atom of Group 14 of the Periodic Table of the Elements represented by J1 include carbon, silicon and germanium atoms. Carbon and silicon atoms are preferable, and a carbon atom is more preferable.
  • Examples of the group having a cyclopentadiene-type anionic skeleton represented by the substituent Cp1 include η5-cyclopentadienyl, η5-methylcyclopentadienyl, η5-dimethylcyclopentadienyl, η5-trimethylcyclopentadienyl, η5-tetramethylcyclopentadienyl, η5-ethylcyclopentadienyl, η5-n-propylcyclopentadienyl, η5-isopropylcyclopentadienyl, η5-n-butylcyclopentadienyl, η5-sec-butylcyclopentadienyl, η5-tert-butylcyclopentadienyl, η5-n-pentylcyclopentadienyl, η5-neopentylcyclopentadienyl, η5-n-hexylcyclopentadienyl, octylcyclopentadienyl, η5-phenylcyclopentadienyl, η5-naphthylcyclopentadienyl, trimethylsilylcyclopentadienyl, η5-triethylsilylcyclopentadienyl, η5-tert-butyldimethylsilylcyclopentadienyl, η5-indenyl, η5-methylindenyl, η5-dimethylindenyl, η5-ethylindenyl, η5-n-propylindenyl, η5-isopropylindenyl, η5-n-butylindenyl, η5-sec-butylindenyl, η5-tert-butylindenyl, η5-n-pentylindenyl, η5-neopentylindenyl, η5-n-hexylindenyl, η5-n-octylindenyl, η5-n-decylindenyl, η5-phenylindenyl, η5-methylphenylindenyl, η5-naphthylindenyl, η5-trimethylsilylindenyl, η5-triethylsilylindenyl, η5-tert-butyldimethylsilylindenyl, η5-tetrahydroindenyl, η5-fluorenyl, η5-methylfluorenyl, η5-dimethylfluorenyl, η5-ethylfluorenyl, η5-diethylfluorenyl, η5-n-propylfluorenyl, η5-di-n-propylfluorenyl, η5-isopropylfluorenyl, η5-diisopropylfluorenyl, η5-n-butylfluorenyl, η5-sec-butylfluorenyl, η5-tert-butylfluorenyl, η5-di-n-butylfluorenyl, η5-di-sec-butylfluorenyl, η5-di-tert-butylfluorenyl, η5-n-pentylfluorenyl, η5-neopentylfluorenyl, η5-n-hexylfluorenyl, η5-n-octylfluorenyl, η5-n-decylfluorenyl, η5-n-dodecylfluorenyl, η5-phenylfluorenyl, η5-di-phenylfluorenyl, η5-methylphenylfluorenyl, η5-naphthylfluorenyl, η5-trimethylsilylfluorenyl, η5-bis-trimethylsilylfluorenyl, η5-triethylsilylfluorenyl and η5-tert-butyldimethylsilylfluorenyl groups. η5-cyclopentadienyl, η5-methylcyclopentadienyl, η5-tert-butylcyclopentadienyl, η5-tetramethylcyclopentadienyl, η5-indenyl and η5-fluorenyl, etc. are preferable.
  • Examples of the halogen atom in X1, X2, R1, R2, R3 and R4 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl and perbromoeicosyl groups.
  • Examples of the aryl group having 6 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tort-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • Examples of the aralkyl group having 7 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyl group listed above with a halogen atom.
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the alkoxy group having 1 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the alkoxy group listed above with a halogen atom.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include aryloxy groups having 6 to 20 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy and anthracenoxy groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aryloxy group having 6 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aryloxy group listed above with a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X1, X2, R1, R2, R3, R4, R5 and R6 include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, (n-tetradecylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxy groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aralkyloxy group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyloxy group listed above with a halogen atom.
  • In the substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, in X1, X2, R1, R2, R3, R4, R5 and R6, the R7s are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); or a halogenated hydrocarbyl group obtained by substituting some or all hydrogen atoms in the hydrocarbyl group with a halogen atom, and the total number of the carbon atoms in the three R7 groups is in the range of 1 to 20. The total number of the carbon atoms in these three R7 groups is preferably in the range of 3 to 18. Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom. Of them, trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of a hydrogen atoms in these groups with a halogen atom are more preferable.
  • In the disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, in X1, X2, R1, R2, R3, R4, R5 and R6, the R8 each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10. The hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as a hydrocarbyl group and a halogenated hydrocarbyl group for the substituted silyl group. Moreover, these two R8 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R8 groups are bonded. Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom. Of these, dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are preferable.
  • Of R1, R2, R3 and R4, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, and R5 and R6 may be bonded to each other to form a ring together with J1 to which R5 and R6 are bonded. Examples of the ring include saturated or unsaturated hydrocarbyl rings and can specifically include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings. These rings may be substituted with a hydrocarbyl group having 1 to 20 carbon atoms, or the like.
  • The substituents X1 and X2 are preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, more preferably a halogen atom.
  • R1 is preferably an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or a substituted silyl group represented by —Si(R7)3 (three R's each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of carbon atoms in three R7s is 1 to 20). Specific examples thereof include methyl, ethyl, isopropyl, tert-butyl, amyl, phenyl, benzyl, trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups. More preferable examples thereof include tert-butyl, trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups.
  • The transition metal complex represented by the general formula (1) can be produced, for example, by a process described in JP 9-87313 A.
  • Examples of the complex represented by the general formula (1) include: transition metal complexes represented by the general formula (1) wherein J1 is a carbon atom, such as methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • isopropylidene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsily)-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tri methyl silylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
  • diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, and diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, and compounds obtained by changing titanium in these compounds into zirconium or hafnium, changing chloride therein into bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide, changing (cyclopentadienyl) therein into (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) or (indenyl), changing 3,5-dimethyl-2-phenoxy therein into 2-phenoxy, 3-methyl-2-phenoxy, 3,5-di-tert-butyl-2-phenoxy, 3-phenyl-5-methyl-2-phenoxy, 3-tert-butyldimethylsilyl-2-phenoxy or 3-trimethylsilyl-2-phenoxy, or changing methylene therein into diethylmethylene; and
  • transition metal complexes represented by the general formula (1) wherein J1 is an atom of Group 14 of the Periodic Table of the Elements other than a carbon atom, such as dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(n-butyl cyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(tert-butylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(indenyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3,5-diamyl-2-phenoxy)titanium dichloride, and dimethylsilylene(tetramethylcyclopentadienyl)(1-naphthoxy-2-yl)titanium dichloride, and compounds obtained by changing (cyclopentadienyl) in these compounds into (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl) or (phenylindenyl), changing 2-phenoxy therein into 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert-butyldimethylsilyl-2-phenoxy, changing dimethylsilylene therein into diethylsilylene, diphenylsilylene or dimethoxysilylene, changing titanium therein into zirconium or hafnium, or changing chloride therein into bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide.
    • <Transition Metal Complex (2)>
  • The catalytic component for trimerization used in the first aspect of the present invention is a transition metal complex represented by the following general formula (2):

  • [Cp2-J2(R9)2—Ar]M2X3X4X5  (2)
  • wherein Cp1 represents a group having a cyclopentadiene-type anionic skeleton; M2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements; J2 represents a carbon atom; Ar represents an aryl group which may have a substituent; R9 represents a hydrocarbyl group which may have a substituent or a hydrogen atom, and
    the two R9 groups may be the same as or different from each other and may be bonded to each other to form ring together with J2; and
    X3, X4 and X5 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, and
    of X3, X4 and X5, two groups may be bonded to each other to form a ring together with M2.
  • The complex represented by the general formula (2) will be described in detail.
  • The group having a cyclopentadiene-type anionic skeleton represented by the substituent Cp1 is a η5-cyclopentadienyl group or a cyclopentadienyl group having at least one substituent. Examples of the cyclopentadienyl group having at least one substituent include η5-methylcyclopentadienyl, η5-dimethylcyclopentadienyl, η5-trimethylcyclopentadienyl, η5-tetramethylcyclopentadienyl, η5-ethylcyclopentadienyl, η5-n-propylcyclopentadienyl, η5-isopropylcyclopentadienyl, η5-n-butylcyclopentadienyl, η5-sec-butylcyclopentadienyl, η5-tert-butylcyclopentadienyl, η5-n-pentylcyclopentadienyl, η5-neopentylcyclopentadienyl, η5-n-hexylcyclopentadienyl, η5-n-octylcyclopentadienyl, η5-phenylcyclopentadienyl, naphthylcyclopentadienyl, η5-trimethylsilylcyclopentadienyl, η5-triethylsilylcyclopentadienyl, η5-tert-butyldimethylsilylcyclopentadienyl, η5-methylindenyl, η5-dimethylindenyl, η5-ethylindenyl, η5-n-propylindenyl, η5-isopropylindenyl, η5-n-butylindenyl, η5-sec-butylindenyl, η5-tert-butylindenyl, η5-n-pentylindenyl, η5-neopentylindenyl, η5-n-hexylindenyl, η5-n-octylindenyl, η5-n-decylindenyl, η5-phenylindenyl, η5-methylphenylindenyl, η5-naphthylindenyl, η5-trimethylsilylindenyl, η5-triethylsilylindenyl, η5-tert-butyldimethylsilylindenyl, η5-tetrahydroindenyl, η5-fluorenyl, η5-methylfluorenyl, η5-dimethylfluorenyl, η5-ethylfluorenyl, η5-diethylfluorenyl, η5-n-propylfluorenyl, η5-di-n-propylfluorenyl, η5-isopropylfluorenyl, η5-diisopropylfluorenyl, η5-n-butylfluorenyl, re-sec-butylfluorenyl, η5-tert-butylfluorenyl, η5-di-n-butylfluorenyl, η5-di-sec-butylfluorenyl, η5-di-tert-butylfluorenyl, η5-n-pentylfluorenyl, η5-neopentylfluorenyl, η5-n-hexylfluorenyl, η5-n-octylfluorenyl, η5-n-decylfluorenyl, η5-n-dodecylfluorenyl, η5-phenylfluorenyl, η5-di-phenylfluorenyl, η5-methylphenylfluorenyl, η5-naphthylfluorenyl, η5-trimethylsilylfluorenyl, η5-bis-trimethylsilylfluorenyl, η5-triethylsilylfluorenyl and η5-tert-butyldimethylsilylfluorenyl groups. The cyclopentadienyl group having at least one substituent is preferably η5-methylcyclopentadienyl, η5-ethylcyclopentadienyl, η5-n-propylcyclopentadienyl, η5-isopropylcyclopentadienyl, η5-n-butylcyclopentadienyl, η5-sec-butylcyclopentadienyl, η5-ten-butylcyclopentadienyl, η5-dimethylcyclopentadienyl, η5-trimethylcyclopentadienyl, η5-tetramethylcyclopentadienyl, η5-indenyl or η5-trimethylsilylcyclopentadienyl group, etc., more preferably η5-methylcyclopentadienyl, η5-ethylcyclopentadienyl, η5-n-propylcyclopentadienyl, η5-isopropylcyclopentadienyl, η5-n-butylcyclopentadienyl, η5-sec-butylcyclopentadienyl, η5-tert-butylcyclopentadienyl, η5-dimethylcyclopentadienyl, η5-trimethylcyclopentadienyl, tetramethylcyclopentadienyl or η5-trimethylsilylcyclopentadienyl group, etc., most preferably η5-trimethylsilylcyclopentadienyl group.
  • J2 is a carbon atom.
  • Examples of the aryl group which may have a substituent represented by Ar include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, anthracenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2,3,4-trimethoxyphenyl, 2,3,5-trimethoxyphenyl, 2,3,6-trimethoxyphenyl, 2,4,6-trimethoxyphenyl, 3,4,5-trimethoxyphenyl, 2,3,4,5-tetramethoxyphenyl, 2,3,4,6-tetramethoxyphenyl, 2,3,5,6-tetramethoxyphenyl, pentamethoxyphenyl, tert-butoxyphenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, 2,3-diphenylphenyl, 2,4-diphenylphenyl, 2,5-diphenylphenyl, 2,6-diphenylphenyl, 3,4-diphenylphenyl, 3,5-diphenylphenyl, 2,3,4-triphenylphenyl, 2,3,5-triphenylphenyl, 2,3,6-triphenylphenyl, 2,4,6-triphenylphenyl, 3,4,5-triphenylphenyl, 2,3,4,5-tetraphenylphenyl, 2,3,4,6-tetraphenylphenyl, 2,3,5,6-tetraphenylphenyl, pentaphenylphenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 4-phenoxyphenyl, 2,3-diphenoxyphenyl, 2,4-diphenoxyphenyl, 2,5-diphenoxyphenyl, 2,6-diphenoxyphenyl, 3,4-diphenoxyphenyl, 3,5-diphenoxyphenyl, 2,3,4-triphenoxyphenyl, 2,3,5-triphenoxyphenyl, 2,3,6-triphenoxyphenyl, 2,4,6-triphenoxyphenyl, 3,4,5-triphenoxyphenyl, 2,3,4,5-tetraphenoxyphenyl, 2,3,4,6-tetraphenoxyphenyl, 2,3,5,6-tetraphenoxyphenyl, pentaphenoxyphenyl, 2-benzylphenyl, 3-benzylphenyl, 4-benzylphenyl, 2,3-dibenzylphenyl, 2,4-dibenzylphenyl, 2,5-dibenzylphenyl, 2,6-dibenzylphenyl, 3,4-dibenzylphenyl, 3,5-dibenzylphenyl, 2,3,4-tribenzylphenyl, 2,3,5-tribenzylphenyl, 2,3,6-tribenzylphenyl, 2,4,6-tribenzylphenyl, 3,4,5-tribenzylphenyl, tetrabenzylphenyl, 2,3,4,6-tetrabenzylphenyl, 2,3,5,6-tetrabenzylphenyl, pentabenzylphenyl, 2-benzyloxyphenyl, 3-benzyloxyphenyl, 4-benzyloxyphenyl, 2,3-dibenzyloxyphenyl, 2,4-dibenzyloxyphenyl, 2,5-dibenzyloxyphenyl, 2,6-dibenzyloxyphenyl, 3,4-dibenzyloxyphenyl, 3,5-dibenzyloxyphenyl, 2,3,4-tribenzyloxyphenyl, 2,3,5-tribenzyloxyphenyl, 2,3,6-tribenzyloxyphenyl, 2,4,6-tribenzyloxyphenyl, 3,4,5-tribenzyloxyphenyl, 2,3,4,5-tetrabenzyloxyphenyl, 2,3,4,6-tetrabenzyloxyphenyl, 2,3,5,6-tetrabenzyloxyphenyl, pentabenzyloxyphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 2,3-bistrimethylsilylphenyl, 2,4-bistrimethylsilylphenyl, 2,5-bistrimethylsilylphenyl, 2,6-bistrimethylsilylphenyl, 3,4-bistrimethylsilylphenyl, 3,5-bistrimethylsilylphenyl, 2,3,4-tristrimethylsilylphenyl, 2,3,5-tristrimethylsilylphenyl, 2,3,6-tristrimethylsilylphenyl, 2,4,6-tristrimethylsilylphenyl, 3,4,5-tristrimethylsilylphenyl, 2,3,4,5-tetrakistrimethylsilylphenyl, 2,3,4,6-tetrakistrimethylsilylphenyl, 2,3,5,6-tetrakistrimethylsilylphenyl, pentatrimethylsilylphenyl, tert-butyldimethylsilylphenyl, triphenylsilylphenyl, 2-dimethylaminophenyl, 3-dimethylaminophenyt, 4-dimethylaminophenyl, 2,3-bisdimethylaminophenyl, 2,4-bisdimethylaminophenyl, 2,5-bisdimethylaminophenyl, 2,6-bisdimethylaminophenyl, 3,4-bisdimethylaminophenyl, 3,5-bisdimethylaminophenyl, 2,3,4-trisdimethylaminophenyl, 2,3,5-trisdimethylaminophenyl, 2,3,6-trisdimethylaminophenyl, 2,4,6-trisdimethylaminosilylphenyl, 3,4,5-trisdimethylaminophenyl, 2,3,4,5-tetrakisdimethylaminophenyl, 2,3,4,6-tetrakisdimethylaminophenyl, 2,3,5,6-tetrakisdimethylaminophenyl, pentadimethylaminophenyl, diethylaminophenyl, pyrrolidinylphenyl and piperidinylphenyl groups.
  • Further examples thereof include groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • The aryl group is preferably a phenyl group or a phenyl group having an alkyl group having 1 to 4 carbon atoms as a substituent, specifically, a 3,5-dimethylphenyl, tetramethylphenyl, n-butylphenyl, sec-butylphenyl or tert-butylphenyl group, etc.
  • Examples of the transition metal atom of Group 4 of the Periodic Table of the Elements (IUPAC Nomenclature of Inorganic Chemistry, Revised, 1989) in M2 include titanium, zirconium and hafnium atoms. Titanium and zirconium atoms are preferable, and a titanium atom is more preferable.
  • Examples of the hydrocarbyl group which may have a substituent in R9 include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups; aralkyl groups such as benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups; and aryl groups such as phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups. Further examples thereof include groups obtained by substituting some or all of hydrogen atoms in these groups with a substituent having a heteroatom such as silicon, nitrogen, phosphorus, oxygen, sulfur and halogen atoms. R9 is preferably a methyl group.
  • The two R9 groups may be bonded to each other to form a ring together with the carbon atoms to which the two R9 groups are bonded. In this context, specific examples of the ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, benzene, naphthalene and anthracene rings.
  • Examples of the halogen atom in X3, X4 and X5 include fluorine, chlorine, bromine and iodine atoms. A chlorine atom is preferable.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X3, X4 and X5 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl and perbromoeicosyl groups.
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X3, X4 and X5 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodecoxy, n-pentadecoxy and n-eicosoxy.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the alkoxy group having 1 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the alkoxy group listed above with a halogen atom.
  • Examples of the aryl group having 6 to 20 carbon atoms in X3, X4 and X5 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X3, X4 and X5 include aryloxy groups having 6 to 20 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy and anthracenoxy groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aryloxy group having 6 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aryloxy group listed above with a halogen atom.
  • Examples of the aralkyl group having 7 to 20 carbon atoms in X3, X4 and X5 include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyl group listed above with a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X3, X4 and X5 include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, (n-tetradecylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxy groups.
  • Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the aralkyloxy group having 7 to 20 carbon atoms having a halogen atom as a substituent include groups obtained by substituting some or all of hydrogen atoms in the aralkyloxy group listed above with a halogen atom.
  • In the substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, in X3, X4 and X5, the R7s are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); or a halogenated hydrocarbyl group obtained by substituting some or all of hydrogen atoms in the hydrocarbyl group with a halogen atom, and the total number of the carbon atoms in the three R7 groups is in the range of 1 to 20. The total number of the carbon atoms in these three R7 groups is preferably in the range of 3 to 18. Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom. Of these, trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are more preferable.
  • In the disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, in X3, X4 and X5, the R8s each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10. The hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as a hydrocarbyl group and a halogenated hydrocarbyl group for the substituted silyl group. Moreover, these two R8 groups may be bonded to each other to form a ring together with the nitrogen atom bonded thereto. Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom. Of these, dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are preferable.
  • Examples of the transition metal complex represented by the general formula (2) include (1-phenylmethyl-cyclopentadienyl)titanium trichloride, (1-diphenylmethyl-cyclopentadienyl)titanium trichloride, (1-triphenylmethyl-cyclopentadienyl)titanium trichloride, [1-(2-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(4-methylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,4-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,5-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,6-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3,4-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3,5-dimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3,4-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3,5-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3,6-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,4,5-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,4,6-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3,4,5-trimethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2,3,4,5,6-pentamethylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(2-trimethylsilylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(3-trimethylsilylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(4-trimethylsilylphenyl)methyl-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2-methylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3-methylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(4-methylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,5-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,6-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,4-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,4-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,5-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,6-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4,5-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4,6-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,4,5-trimethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,4,5,6-pentamethylphenyl)ethyl)-cyclopentadienyl]titanium trichloride, [1-(1-ethyl-1-phenylpropyl)-cyclopentadienyl]titanium trichloride, [1-(1-phenylcyclohexyl)-cyclopentadienyl]titanium trichloride, [1-(1-phenylvinyl)-cyclopentadienyl]titanium trichloride,
  • [1-phenylmethyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-diphenylmethyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-triphenylmethyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2-methylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(3-methylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(4-methylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,3-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,4-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,5-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,6-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(3,4-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(3,5-dimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,3,4-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,3,5-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,3,6-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,4,5-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,4,6-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(3,4,5-trimethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2,3,4,5,6-pentamethylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(2-trimethylsilylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(3-trimethylsilylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(4-trimethylsilylphenyl)methyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-phenylethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2-methylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3-methylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(4-methylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,6-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,4-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,4-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,5-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,6-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4,5-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,4,6-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(3,4,5-trimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-methyl-1-(2,3,4,5,6-pentamethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, [1-(1-ethyl-1-phenylpropyl)-cyclopentadienyl]titanium trichloride, [1-(1-phenylcyclohexyl)-cyclopentadienyl]titanium trichloride, and [1-(1-phenylvinyl)-cyclopentadienyl]titanium trichloride, and compounds in which cyclopentadienyl in these compounds are replaced with 2-methylcyclopentadienyl, 3-methylcyclopentadienyl, 2,3-dimethyl cyclopentadienyl, 2,4-dimethylcyclopentadienyl, 2,5-dimethylcyclopentadienyl, 2,3,4-trimethylcyclopentadienyl, 2,3,5-trimethylcyclopentadienyl, 2,3,4,5-tetramethylcyclopentadienyl, 2-n-butylcyclopentadienyl, 3-n-butylcyclopentadienyl, 2,3-di-n-butylcyclopentadienyl, 2,4-di-n-butylcyclopentadienyl, 2,5-di-n-butylcyclopentadienyl, 2,3,4-tri-n-butylcyclopentadienyl, 2,3,5-tri-n-butylcyclopentadienyl, 2,3,4,5-tetra-n-butylcyclopentadienyl, 2-tert-butylcyclopentadienyl, 3-tert-butylcyclopentadienyl, 2,3-di-tert-butylcyclopentadienyl, 2,4-di-tert-butylcyclopentadienyl, 2,5-di-tert-butylcyclopentadienyl, 2,3,4-tri-tert-butylcyclopentadienyl, 2,3,5-tri-tert-butylcyclopentadienyl, 2,3,4,5-tetra-tert-butylcyclopentadienyl, 2-trimethylsilylcyclopentadienyl, 3-trimethylsilylcyclopentadienyl, 2,3-di-trimethylsilylcyclopentadienyl, 2,4-di-trimethylsilylcyclopentadienyl, 2,5-di-trimethylsilylcyclopentadienyl, 2,3,4-tris(trimethylsilyl)cyclopentadienyl, 2,3,5-tris(trimethylsilyl)cyclopentadienyl, 2,3,4,5-tetrakis(trimethylsilyl)cyclopentadienyl, indenyl or fluorenyl; titanium therein is replaced with zirconium or hafnium; or chloride therein is replaced with bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide.
  • The transition metal complex represented by the general formula (2) can be produced, for example, by a process described in Organometallics 2002, 21, pp 5122-5135.
    • <Transition Metal Complex (3)>
  • The catalytic component for trimerization used in the second aspect of the present invention is a transition metal complex represented by the following general formula (3):
  • Figure US20120184693A1-20120719-C00005
  • wherein
    M3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
    R10, R11, R12, R13 and R14 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    R15 and R16 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    X6, X7 and X8 each independently represent
    a hydrogen atom, a halogen atom,
    an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
    a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
    a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
    of R10, R11, R12, R13 and R14, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X6, X7 and X8 may be bonded to each other to form a ring together with M3; and R15 and R16 may be bonded to each other to form a ring together with the silicon atom to which R15 and R16 are bonded.
  • Hereinafter, the transition metal complex represented by the general formula (3) will be described in detail.
  • In the transition metal complex (3), M3 represents an element of Group 4 of the Periodic Table of the Elements, and examples thereof include titanium, zirconium and hafnium atoms. Among them, a titanium atom is preferable.
  • In the transition metal complex (3), the substituents R10, R11, R12, R13, R14, R15, R16, X6, X7 and X8 are as defined above, and specific examples thereof are shown below.
  • The halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.
  • Specific examples of the “alkyl group having 1 to 20 carbon atoms” in the alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and n-eicosyl groups. Of these, the preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof can include methyl, ethyl, isopropyl, tert-butyl and amyl groups. Moreover, the phrase “may have a halogen atom as a substituent” in the “alkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkyl group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above. When the alkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10. Preferable examples of the alkyl group having a halogen atom as a substituent can include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexyl groups.
  • Specific examples of the “aryl group having 6 to 20 carbon atoms” in the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups. Of these, the preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof include a phenyl group. Moreover, the phrase “may have a halogen atom as a substituent” in the “aryl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryl group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above. When the aryl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10. Preferable examples of the aryl group having a halogen atom as a substituent specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • Specific examples of the “aralkyl group having 7 to 20 carbon atoms” in the aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups. Of these, the preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof include a benzyl group. Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyl group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyl group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above. When the aralkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • Specific examples of the “alkoxy group having 1 to 20 carbon atoms” in the alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups. Of these, the preferable alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and more preferable examples thereof can include methoxy, ethoxy and tert-butoxy groups. Moreover, the phrase “may have a halogen atom as a substituent” in the “alkoxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the alkoxy group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above. When the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.
  • Specific examples of the “aryloxy group having 6 to 20 carbon atoms” in the aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy and anthracenoxy groups. Of these, the preferable aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and more preferable examples thereof can include phenoxy, 2-methylphenoxy, 3-methylphenoxy and 4-methylphenoxy groups. Moreover, the phrase “may have a halogen atom as a substituent” in the “aryloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aryloxy group may be substituted with a halogen atom. Specific examples of the halogen atom are as described above. When the aryloxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • Specific examples of the “aralkyloxy group having 7 to 20 carbon atoms” in the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxy groups. Of these, the preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyloxy group. Moreover, the phrase “may have a halogen atom as a substituent” in the “aralkyloxy group which may have a halogen atom as a substituent” means that some or all of hydrogen atoms in the aralkyloxy group may be substituted with by a halogen atom. Specific examples of the halogen atom are as described above. When the aralkyloxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • In the substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, the R7 groups are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); or a halogenated hydrocarbyl group obtained by substituting some or all hydrogen of atoms in the hydrocarbyl group with a halogen atom, and the total number of the carbon atoms in the three R7 groups is in the range of 1 to 20. The total number of the carbon atoms in these three R7 groups is preferably in the range of 3 to 18. Specific examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in the hydrocarbyl groups listed above with a halogen atom. Of these, trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are more preferable.
  • In the disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, the R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is in the range of 2 to 20, more preferably in the range of 2 to 10. The hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as the hydrocarbyl group and the halogenated hydrocarbyl group for the substituted silyl group. Moreover, these two R8 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R8 groups are bonded. Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom. Of these, dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, and groups obtained by substituting some or all of hydrogen atoms in these groups with a halogen atom are preferable.
  • R15 and R16 may be bonded to each other to form a ring together with the silicon atom to which R15 and R16 are bonded, and of R10, R11, R12, R13 and R14, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which the two groups are bonded. In this context, the ring can be a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, or the like. Specific examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings.
  • In the transition metal complex (3), R10, R11, R12, R13 and R14 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.
  • Examples of a preferable combination of R10, R11, R12, R13 and R14 can include those that can provide the following substructures represented by a substructural formula (4):
  • Figure US20120184693A1-20120719-C00006
  • wherein R10, R11, R12, R13 and R14 are as defined above:
  • phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl and bis(trifluoromethyl)phenyl.
  • Of the substructures exemplified above, the preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, pentamethylphenyl or the like.
  • In the transition metal complex (3), R15 and R16 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, naphthyl and benzyl group.
  • Examples of a preferable combination of R15 and R16 can include those that can provide the following substructures represented by a substructural formula (5):
  • Figure US20120184693A1-20120719-C00007
  • wherein R15 and R16 are as defined above:
  • dimethylsilylene, diethylsilylene, ethylmethylsilylene, di(n-propyl)silylene, methyl(n-propyl)silylene, di(n-butyl)silylene, n-butylmethylsilylene, diphenylsilylene and methylphenylsilylene.
  • Of the silylene substructures exemplified above, the preferable silylene substructure is dimethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclotetramethylenesilylene, or the like.
  • Specific examples of the transition metal complex (3) can include the following complexes:
  • [1-dimethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-diethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-cyclotetramethylene(phenyl)silyl-cyclopentadienyl]titanium trichloride, [1-ethylmethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-n-butylmethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-n-butylmethyl(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride, [1-n-butylmethyl(2,4,6-trimethylphenyl)silyl-cyclopentadienyl]titanium trichloride and [1-n-butylmethyl(pentamethylphenyl)silyl-cyclopentadienyl]titanium trichloride. Further examples thereof include complexes in which “titanium” in these complexes exemplified above is replaced with “zirconium” or “hafnium”, or “chloride” therein with “fluoride”, “bromide”, “iodide”, “hydride”, “methyl”, “phenyl”, “benzyl”, “methoxide”, “n-butoxide”, “isopropoxide”, “phenoxide”, “benzyloxide”, “dimethylamide” or “diethylamide”.
  • The transition metal complex represented by the general formula (3) can be produced, for example, by process described in J. Organomet. Chem. 1999, 592, pp 84-94.
    • <Activating Co-Catalytic Component>
  • Examples of the activating co-catalytic component can include compounds (A) and (B) shown below. These compounds (A) and (B) may be used in combination:
  • Compound (A): one or more aluminum compounds selected from the compound group consisting of the following compounds (A1) to (A3):
  • (A1): an organic aluminum compound represented by a general formula (E1)aAl(G)3-a,
  • (A2): a cyclic aluminoxane having a structure represented by a general formula {—Al(E2)—O—}b, and
  • (A3): a linear aluminoxane having a structure represented by a general formula E3{—Al(E3)—O—}cAl(E3)2, wherein
  • E1, E2 and E3 represent a hydrocarbyl group having 1 to 8 carbon atoms; G represents a hydrogen atom or a halogen atom; a represents an integer of 1 to 3; b represents an integer of 2 or more; c represents an integer of 1 or more; E1 groups may be the same or different from each other when more than one E1 groups exist; G groups may be the same or different from each other when one or more G groups exist; E2 groups may be the same or different from each other; and E3 groups may be the same or different from each other.
    Compound (B): one or more boron compounds selected from the compound group consisting of the following compounds (B1) to (B3):
  • (B1): a boron compound represented by a general formula BQ1Q2Q3,
  • (B2): a borate compound represented by a general formula T+(BQ1Q2Q3Q4)−, and
  • (B3): a borate compound represented by a general formula (L-H)+(BQ1Q2Q3Q4)−, wherein
  • B represents a trivalent boron atom; Q1, Q2, Q3 and Q4 are the same as or different from each other and each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a hydrocarbylsilyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a dihydrocarbylamino group having 2 to 20 carbon atoms; T+ represents an inorganic or organic cation; and (L-H)+ represents a Broensted acid.
  • In the compounds (A1) to (A3), examples of the hydrocarbyl group having 1 to 8 carbon atoms in E1, E2 and E3 include alkyl having 1 to 8 carbon atoms. Examples of the alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl group.
  • Examples of the organic aluminum compound (A1) represented by the general formula (E1)aAl(G)3-a, include trialkylaluminums, dialkylaluminum chlorides, alkylaluminum dichlorides and dialkylaluminum hydrides. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum. Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride. Examples of the alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
  • These aluminoxanes are prepared by various methods. The methods are not particularly limited, and they may be prepared according to methods known in the art. For example, a solution containing a trialkylaluminum (e.g., trimethylaluminum) dissolved in an appropriate organic solvent (e.g., benzene or aliphatic hydrocarbyl) is contacted with water to prepare the aluminoxanes. Another preparation method can involve, for example, contacting a trialkylaluminum (e.g., trimethylaluminum) with a metal salt (e.g., copper sulfate hydrate) containing crystalline water.
  • Examples of E2 and E3 in (A2): a cyclic aluminoxane having a structure represented by the general formula {—Al(E2)—O-}n and (A3): a linear aluminoxane having a structure represented by the general formula E3{—Al(E3)—O-}cAl(E3)2 include alkyl groups such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl groups. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E2 and E3 are each independently a methyl group or an isobutyl group, b is 2 to 40, and C is 1 to 40.
  • In the compounds (B1) to (B3), Q1, Q2, Q3 and Q4 are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom. Examples of the inorganic cation in T+ include ferrocenium cation, alkyl-substituted ferrocenium cations and silver cation. Examples of the organic cation in T+ include triphenylmethyl cation. Examples of (BQ1Q2Q3Q4)− include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate and tetrakis(3,5-bistrifluoromethylphenyl)borate. Examples of the Broensted acid represented by (L-H)+ include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium and triarylphosphonium.
  • Examples of the boron compound (B1) represented by the general formula BQ1Q2Q3 include 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 and phenylbis(pentafluorophenyl)borane.
  • Examples of the borate compound (B2) represented by the general formula T+(BQ1Q2Q3Q4)− include ferrocenium tetrakis(pentafluorophenyl)borate, 1,1′-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate.
  • Examples of the borate compound (B3) represented by the general formula (L-H)+(BQ1Q2Q3Q4)− include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate and tri(bis-trimethylsilylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.
    • <Olefin Polymerization Catalyst>
  • The olefin polymerization catalyst used in the first aspect of the present invention is a catalyst obtainable by bringing the catalytic component for olefin polymerization comprising the transition metal complex represented by the general formula (1), the catalytic component for trimerization comprising the transition metal complex represented by the general formula (2) and the activating co-catalytic component into contact with each other.
  • The olefin polymerization catalyst used in the second aspect of the present invention is a catalyst obtainable by bringing the catalytic component for olefin polymerization, the catalytic component for trimerization comprising the transition metal complex represented by the general formula (3) and the activating co-catalytic component into contact with each other.
  • Regarding the amount of each catalytic component used, the molar ratio between the catalytic component for trimerization and the catalytic component for olefin polymerization (catalytic component for trimerization/catalytic component for olefin polymerization) is usually 0.0001 to 100, preferably 0.001 to 1, more preferably 0.01 to 0.5, even more preferably 0.05 to 0.15.
  • Regarding the amount of each catalytic component used, the molar ratio between the compound (A) (in terms of the aluminum atom) and the transition metal complexes used as catalytic components (total of the catalytic component for trimerization and the catalytic component for olefin polymerization) (compound (A) (in terms of the aluminum atom)/transition metal complexes) is usually 0.01 to 10000, preferably 5 to 2000. Moreover, the molar ratio between the compound (B) and the transition metal complexes used as catalytic components (total of the catalytic component for trimerization and the catalytic component for olefin polymerization) (compound (B)/transition metal complexes) is usually 0.01 to 100, preferably 0.5 to 10.
  • When each catalytic component is used in a solution state, the concentration of the transition metal complex used as a catalytic component is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L. The concentration of the compound (A) is usually 0.01 to 500 mmol/L, preferably 0.1 to 100 mmol/L, in terms of the aluminum atom. The concentration of the compound (B) is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • Each catalytic component may be supported by a carrier for use. A porous substance is preferably used as a carrier. More preferably an inorganic substance or an organic polymer, even more preferably an inorganic substance, is used. The carrier will be described later.
  • The method for bringing each catalytic component into contact with each other is not particularly limited. The catalytic component for olefin polymerization, the catalytic component for trimerization and the activating co-catalytic component may be brought into contact with each other in advance to prepare a polymerization catalyst, which is then supplied to a polymerization reactor. Alternatively, these catalytic components may be supplied to a polymerization reactor in any order and subjected to contact treatment in the polymerization reactor. The catalytic component for olefin polymerization brought into contact with the catalytic component for trimerization in advance (including those in which the catalytic component for olefin polymerization and the catalytic component for trimerization are produced simultaneously) may also be supplied to a polymerization reactor. Alternatively, the catalytic component for olefin polymerization brought into contact with the activating co-catalytic component in advance may be supplied thereto. Further alternatively, the catalytic component for trimerization brought into contact with the activating co-catalytic component in advance may be supplied thereto.
    • (Carrier)
  • Examples of the inorganic substance used as a carrier include inorganic oxides and magnesium compounds. Clay, clay mineral, or the like may also be used. They may be mixed for use.
  • Specific examples of the inorganic oxides used as a carrier can include SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2 and mixtures thereof, for example, SiO2—MgO, SiO2—Al2O3, SiO2—TiO2, SiO2—V2O5, SiO2—Cr2O3 and SiO2—TiO2—MgO. Among these inorganic oxides, SiO2 and Al2O3 are preferable, and SiO2 is more preferable. These inorganic oxides may contain a small amount of a carbonate, sulfate, nitrate or oxide component such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.
  • Moreover, the inorganic oxides usually have a hydroxy group formed on its surface. Modified inorganic oxides obtained by substituting active hydrogen in the surface hydroxy group with various substituents may be used as the inorganic oxides, and a preferable substituent is a silyl group. Specific examples of the modified inorganic oxides include inorganic oxides treated by contact with a trialkylchlorosilane such as trimethylchlorosilane and tertbutyldimethylchlorosilane, a triarylchlorosilane such as triphenylchlorosilane, a dialkyldichlorosilane such as dimethyldichlorosilane, a diaryldichlorosilane such as diphenyldichlorosilane, an alkyltrichlorosilane such as methyltrichlorosilane, an aryltrichlorosilane such as phenyltrichlorosilane, a trialkylalkoxysilane such as trimethylmethoxysilane, a triarylalkoxysilane such as triphenylmethoxysilane, a dialkyldialkoxysilane such as dimethyldimethoxysilane, a diaryldialkoxysilane such as diphenyldimethoxysilane, an alkyltrialkoxysilane such as methyltrimethoxysilane, an aryltrialkoxysilane such as phenyltrimethoxysilane, a tetraalkoxysilane such as tetramethoxysilane, an alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, or the like.
  • Examples of the magnesium compounds used as a carrier can include: a magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; an alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride; an aryloxy magnesium halide such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; an alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; an aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and a carboxylate of magnesium such as magnesium laurate and magnesium stearate. Among them, a magnesium halide or an alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.
  • Examples of the clay or clay mineral used as a carrier include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc, micas isinglass, montmorillonites, vermiculite, chlorites, palygorskite, kaolinite, nacrite, dickite halloysite, and son on. Among these, smectite, a montmorillonite, hectorite, Laponite or saponite is preferable, and a montmorillonite or hectorite is more preferable.
  • The inorganic substance used as a carrier is preferably inorganic oxide.
  • These inorganic substances used as a carrier are preferably dried, for use, by heat treatment. The temperature of the heat treatment is usually 100 to 1500° C., preferably 100 to 1000° C., more preferably 200 to 800° C. The time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the method for the heat treatment include, but not limited to, a method in which after heating, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • The average particle size of the carrier comprising the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, even more preferably 10 to 100 p.m. The pore volume of the carrier comprising the inorganic substance is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g. The specific surface of the carrier comprising the inorganic substance is preferably 10 to 1000 m2/g, more preferably 100 to 500 m2/g.
  • The organic polymer used as a carrier is not particularly limited, and two or more organic polymers may be used as a mixture. A polymer having a group having active hydrogen and/or a non-proton-donating Lewis-basic group is preferable.
  • The group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples thereof include primary amino, secondary amino, imino, amide, hydrazide, amidino, hydroxy, hydroperoxy, carboxyl, formyl, carbamoyl, sulfonic acid, sulfinic acid, sulfenic acid, thiol, thioformyl, pyrrolyl, imidazolyl, piperidyl, indazolyl and carbazolyl groups. A primary amino, secondary amino, imino, amide, imide, hydroxy, formyl, carboxyl, sulfonic acid or thiol group is preferable. A primary amino, secondary amino, amide or hydroxy group is particularly preferable. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • The non-proton-donating Lewis-basic group is not particularly limited as long as it is a group having a Lewis base moiety free from an active hydrogen atom. Specific examples thereof include pyridyl, N-substituted imidazolyl, N-substituted indazolyl, nitrile, azide, N-substituted imino, N,N-substituted amino, N,N-substituted aminooxy, N,N,N-substituted hydrazino, nitroso, nitro, nitrooxy, furyl, carbonyl, thiocarbonyl, alkoxy, alkyloxycarbonyl, N,N-substituted carbamoyl, thioalkoxy, substituted sulfinyl, substituted sulfonyl and substituted sulfonic acid groups. Heterocyclic groups are preferable, and aromatic heterocyclic groups having oxygen and/or nitrogen atoms in the ring are more preferable. A pyridyl, N-substituted imidazolyl or N-substituted indazolyl group is particularly preferable, with a pyridyl group most preferred. These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • The amount of the group having active hydrogen and the non-proton-donating Lewis-basic group in the polymer is preferably 0.01 to 50 mmol/g, more preferably 0.1 to 20 mmol/g, in terms of the molar amount of the group per unit gram of the polymer.
  • The polymer having such group(s) can be obtained, for example, by homopolymerizing monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups or by copolymerizing such a monomer with additional monomer(s) having one or more polymerizable unsaturated groups. Moreover, a polymerizable crosslinking monomer having two or more polymerizable unsaturated groups is preferably used as at least one of the additional monomers.
  • Examples of such monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups can include monomers having the group having active hydrogen and one or more polymerizable unsaturated groups, and monomers having the group having a Lewis base moiety free from an active hydrogen atom and one or more polymerizable unsaturated groups. Examples of such polymerizable unsaturated groups include: alkenyl groups such as vinyl and allyl; and alkynyl groups such as an ethyne group.
  • Examples of the monomers having the group having active hydrogen and one or more polymerizable unsaturated groups can include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds and vinyl group-containing hydroxy compounds. Specific examples thereof include N-(1-ethenyl)amine, N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine, N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide, N-methyl-(1-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol, 2-propen-1-ol and 3-buten-1-ol.
  • Specific examples of the monomers having the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups can include vinylpyridine, vinyl (N-substituted) imidazole and vinyl (N-substituted) indazole.
  • Examples of the additional monomers having one or more polymerizable unsaturated groups include olefin and aromatic vinyl compounds and specifically include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and styrene. Ethylene or styrene is preferable. These monomers may be used in combination of two or more thereof. Moreover, specific examples of the polymerizable crosslinking monomer having two or more polymerizable unsaturated groups include divinylbenzene.
  • The average particle size of the carrier comprising the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 μm. The pore volume of the carrier comprising the organic polymer is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g. The specific surface of the carrier comprising the organic polymer is preferably 10 to 1000 m2/g, more preferably 50 to 500 m2/g.
  • These organic polymers used as a carrier are preferably dried, for use, by heat treatment. The temperature of the heat treatment is usually 30 to 400° C., preferably 50 to 200° C., more preferably 70 to 150° C. The time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the method for the heat treatment include, but not limited to, a method in which after heating, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • The geometric standard deviation of the particle size of the carrier based on the volume is preferably 2.5 or lower, more preferably 2.0 or lower, even more preferably 1.7 or lower.
    • <Polymerization>
  • The present invention relates to a process for producing an ethylenic polymer, comprising polymerizing ethylene in the presence of the olefin polymerization catalyst. The polymerization may be performed by supplying only ethylene as a raw material monomer or by supplying an ethylene-copolymerizable monomer and ethylene.
  • Examples of the ethylene-copolymerizable monomer include: olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 4-methyl-1-hexene; cyclic olefins such as norbornene; alkenyl aromatic hydrocarbyl compounds such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate; and vinyl ester compounds such as vinyl acetate. These monomers may be used alone or in combination of two or more thereof.
  • The polymerization process is not particularly limited and can be, for example, solvent polymerization or slurry polymerization using aliphatic hydrocarbyl (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbyl (benzene, toluene, etc.) or hydrocarbyl halide (methylene dichloride, etc.) as a solvent, or gas-phase polymerization carried out in monomers in gas phase, or the like. Moreover, both continuous polymerization and batch polymerization can be carried out.
  • The present invention can produce a polymer having a butyl branch and having a lowered melting point even by polymerization using hexene supplied in small amounts as a raw material monomer or by polymerization using only ethylene supplied as a raw material monomer. Therefore, polymerization conditions that make the advantages of the present invention more significant involve an ethylene molar fraction (the total amount of ethylene and 1-hexene in the polymerization system is defined as 100 mol %) of preferably 90 mol % or larger, more preferably 95 mol % or larger, even more preferably, substantially 100 mol %, in the polymerization system, when the polymerization form is slurry polymerization. Moreover, when the polymerization form is gas-phase polymerization, the ethylene molar fraction (the total amount of ethylene and 1-hexene in the polymerization system is defined as 100 mol %) is preferably 97 mol % or larger, more preferably 98 mol % or larger, even more preferably, substantially 100 mol %, in the polymerization system.
  • For the solution polymerization and the slurry polymerization, the concentration of the olefin polymerization catalyst in the polymerization solution is usually 0.0001 to 5 mmol/L in terms of the mole of the transition metal complexes used as catalytic components (total of the catalytic component for trimerization and the catalytic component for olefin polymerization). The concentration of the olefin polymerization catalyst is preferably 2 mmol/L or lower, more preferably 1 mmol/L or lower, to improve the economical efficiency. Moreover, the concentration of the olefin polymerization catalyst is preferably 0.001 mmol/L or higher, more preferably 0.01 mmol/L or higher, even more preferably 0.1 mmol/L or higher, particularly preferably 0.5 mmol/L or higher, for lowering the melting point and further increasing the butyl branches.
  • The polymerization pressure is preferably from the normal pressure to 5 MPa. The polymerization time is generally determined according to the type of the polymer of interest and a reaction apparatus as appropriate, and can be in the range of 1 minute to 20 hours. Moreover, a chain transfer agent such as hydrogen can also be added for controlling the molecular weight of the ethylenic polymer.
  • The polymerization temperature can be in the range of 0° C. to 220° C. The polymerization temperature is preferably 20° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, most preferably 70° C. or higher, to improve the economic efficiency. Moreover, the polymerization temperature is preferably 130° C. or lower, more preferably 100° C. or lower, for lowering the melting point and further increasing the butyl branches.
    • <Polymer>
  • Examples of the ethylenic polymer obtained by the production process of the present invention include ethylene-1-hexene, ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene, ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene, ethylene-1-hexene-1-butene-1-octene, ethylene-1-hexene-1-butene-4-methyl-1-pentene, ethylene-1-hexene-styrene, ethylene-1-hexene-norbornene, ethylene-1-hexene-propylene-styrene and ethylene-1-hexene-propylene-norbornene copolymers.
  • The ethylenic polymer is preferably an ethylene-1-hexene, ethylene-1-hexene-propylene, ethylene-1-hexene-1-butene, ethylene-1-hexene-1-octene, ethylene-1-hexene-4-methyl-1-pentene, ethylene-1-hexene-styrene or ethylene-1-hexene-norbornene copolymer, more preferably an ethylene-1-hexene or ethylene-1-hexene-1-butene copolymer.
  • The number of butyl branches per 1000 carbon atoms in the ethylenic polymer is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 10 or more, from the viewpoint of improving the mechanical strength of the ethylenic polymer. Moreover, the number of butyl branches is preferably 40 or less, more preferably 30 or less, even more preferably 25 or less, from the viewpoint of enhancing the stiffness of the ethylenic polymer. The number of butyl branches can be determined by a method such as carbon nuclear magnetic resonance (13C-NMR) or IR spectroscopy.
  • The melting point of the ethylenic polymer is preferably lower than 130° C. from the viewpoint of improving the mechanical strength of the ethylenic polymer. The melting point can be determined using a differential scanning calorimeter.
  • The number of butyl branches per 1000 carbon atoms in the ethylenic polymer can be increased by increasing a molar ratio between the catalytic component for trimerization and the catalytic component for olefin polymerization (catalytic component for trimerization/catalytic component for olefin polymerization) used in the preparation of the polymerization catalyst or by lowering the polymerization temperature.
  • The molecular weight distribution (Mw/Mn) of the ethylenic polymer is preferably 1.5 or higher for improving the processability of the polymer. Moreover, Mw/Mn is preferably 20 or lower for improving the mechanical strength of the polymer. The molecular weight distribution (Mw/Mn) is a value (Mw/Mn) obtained by deviding the weight-average molecular weight (Mw) by the number-average molecular weight (Mn) both determined by gel permeation chromatography in terms of polystyrene standards.
  • The ethylenic polymer is molded, for use, into various types of moldings (e.g., films, sheets and containers (bottles, trays, etc.)) by a molding method known in the art, for example: extrusion methods such as inflation film molding and T-die film molding; hollow molding, injection molding; compression molding; and cross-linked foaming molding.
  • The ethylenic polymer may be blended with a resin known in the art and then molded. Moreover, the moldings may be a monolayer molding containing the ethylenic polymer or may be a multilayer molding comprising a layer containing the ethylenic polymer.
  • Examples of the moldings include films for food package, containers for food package, packaging materials for pharmaceuticals, surface-protective films, packaging materials for electronic parts used in packages for semiconductor products or the like, cross-linked foamed moldings, injection foamed moldings, hollow moldings, blow bottles and squeeze bottles.
    • EXAMPLES
  • The present invention will be described by way of the following Examples and Comparative Examples.
    • <Production of Ethylenic Polymer>
  • Measurement values of each item in Examples and Comparative Examples were measured according to methods shown below. If necessary, an appropriate amount (e.g., 1000 ppm) of an antioxidant was formulated to measurement samples in advance.
    • (1) Molecular Weight and Molecular Weight Distribution (Mw/Mn)
  • Measurement was performed under the following conditions using Rapid GPC (manufactured by Symyx Technologies, Inc.):
      • Liquid feeding apparatus: (LC pump) manufactured by Gilson, Inc.
        • Model 305 (pump head 25.5C)
      • Column: PL gel Mixed-B 10 μm
        • manufactured by Polymer Laboratories (PL), Inc.
        • 7.5 mm in diameter×300 mm
      • Mobile phase: o-dichlorobenzene
      • Dissolving solvent: 1,2,4-trichlorobenzene
      • Flow rate: 2 ml/min.
      • Column temperature: 160° C.
      • Calibration curve: 8 samples Polystyrene (PS) of PL Standard
        • (Standard PS molecular weights) 5,000, 10,050,
        • 28,500, 65,500, 185, 400, 483,000, 1,013,000,
        • 3,390,000
          (2) Melting point (unit: ° C.)
  • The melting point of the polymer was measured under the following conditions using a differential scanning calorimeter (DSC6200R, manufactured by Seiko Instruments Inc.). The melting point was determined from a thermogram in the second heating.
  • [Conditions] 20° C. (20° C./min.)→200° C. (held for 10 minutes)(−20° C./min.)→−100° C. (held for 10 minutes)(20° C./min.)→200° C. (held for 10 minutes)
    • (3) The Number of Butyl Branches
  • The number of butyl branches in the obtained polymer was determined from the infrared absorption spectra. In this context, the measurement and the calculation were performed using hexene-derived characteristic absorption according to a method described in a literature (Characterization of Polyethylene based on Infrared Absorption Spectra, Takayama, Usami, et al.). The number of butyl branches was indicated in terms of the number of branches per 1000 carbon atoms (Me/1000 C).
    • Example 1
  • In an autoclave, toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO, manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, a toluene solution (900 μL) of 0.01 μmol of [1-(1-methyl-1-phenylsilyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 μmol of dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 2) was supplied to the autoclave to initiate the polymerization. The polymerization was performed at 70° C. for 3 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene in the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 47.4×106 g per 1 mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, Mw was 4.3×105, Mw/Mn was 1.9, the melting point was 128.1° C. and the number of butyl brahcnes was 2. The results are shown in Table 1.
    • Example 2
  • In an autoclave, toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to in the autoclave. Then, 900 μL of a toluene solution containing 0.005 μmol of [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride (complex 3) and 0.095 μmol of dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 2) was supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 3 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 49.9×106 g per 1 mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, Mw was 4.4×105, Mw/Mn was 2.0, the melting point was 127.5° C. and the number of butyl brahcnes was 3. The results are shown in Table 1.
    • Example 3
  • In an autoclave, toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C. and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to in the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride (complex 3) and 0.09 μmol of dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 2) was supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 5 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 33.1×106 g per 1 mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, Mw was 4.6×106, Mw/Mn was 2.0, the melting point was 122.5° C. and the number of butyl brahcnes was 5. The results are shown in Table 1,
    • Example 4
  • In an autoclave, 1-hexene (0.02 ml) and toluene (3.7 ml) were placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 μmol of dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 2) was supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 9 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 12.9×106 g per 1 mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, Mw was 2.8×105, Mw/Mn was 2.3, the melting point was 113.0° C. and the number of butyl branches was 10. The results are shown in Table 1.
    • Example 5
  • In an autoclave, toluene (3.64 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (160 μL) of triisobutylaluminum having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride (complex 3) and 0.09 μmol of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (complex 4) and 300 μL of a toluene solution containing triphenylmethyl tetrakis(pentafluorophenyl)borate at a concentration of 0.001 mmol/mL were supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 51 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 0.94×106 g per 1 mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, Mw was 2.1×105, Mw/Mn was 1.5, the melting point was 129.2° C. and the number of butyl branches was 5. The results are shown in Table 2.
    • Comparative Example 1
  • In an autoclave, toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 μmol of dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride (complex 5) was supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 8 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 21.1×106 g per mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, the melting point was 132.4° C.
  • The results are shown in Table 1.
    • Comparative Example 2
  • In an autoclave, toluene (3.7 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (400 μL) of methylaluminoxane (TMAO manufactured by Tosoh Finechem Corp.) having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 mmol of ethylene(bisindenyl)zirconium dichloride (complex 6) was supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 6 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 34.4×106 g per mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, the melting point was 132.8° C.
  • The results are shown in Table 1.
    • Comparative Example 3
  • In an autoclave, toluene (3.64 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (160 μL) of triisobutylaluminum having a concentration of 0.25 mmol/mL was supplied to the autoclave. Then, 900 μL of a toluene solution containing 0.01 mmol of [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 μmol of dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride (complex 5) and 300 μL of a toluene solution containing N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate at a concentration of 0.001 mmol/mL were supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 6 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 23.1×106 g per mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, the melting point was 134.5° C.
  • The results are shown in Table 2.
    • Comparative Example 4
  • In an autoclave, toluene (3.64 ml) was placed under a nitrogen atmosphere. The interior temperature was increased to 70° C., and ethylene was pressurized to 0.60 MPa to stabilize the system. Then, a toluene solution (160 μL) of triisobutylaluminum having a concentration of 0.25 mmol/mL, was supplied to in the autoclave. Then, 900 μL of a toluene solution containing 0.01 μmol of [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride (complex 1) and 0.09 μmol of dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride (complex 5) and 300 μL of a toluene solution containing triphenylmethyl tetrakis(pentafluorophenyl)borate at a concentration of 0.001 mmol/mL were supplied to the autoclave to initiate the polymerization, which was performed at 70° C. for 2 minutes. During the polymerization, ethylene gas was supplied so as to maintain the whole pressure of the autoclave at a constant value. After the completion of the polymerization, the ethylene within the autoclave was purged and the volatile component therein was removed by distillation under reduced pressure to obtain a polymer. The activity was 63.0×106 g per mol of a transition metal complex per hour.
  • The physical properties of the resultant polymer were measured, the melting point was 134.8° C.
  • The results are shown in Table 2.
  • TABLE 1
    Time polym. trim. trim. cat Me/ act × 106
    min cocat cat cat. mol % Tm(° C.) 1000 C g/molh Mw Mw/Mn
    Example 1 3 TMAO(tol) 2 1 10 128.1 2 47.4 430000 1.9
    Example 2 3 TMAO(tol) 2 3 5 127.5 3 49.9 440000 2.0
    Example 3 5 TMAO(tol) 2 3 10 122.5 5 33.1 460000 2.0
    Example 4 9 TMAO(tol) 2 1 10 113.0 10 12.9 280000 2.3
    Comparative 8 TMAO(tol) 5 1 10 132.4 — 21.1 — —
    Example 1
    Comparative 6 TMAO(tol) 6 1 10 132.8 — 34.4 — —
    Example 2
  • TABLE 2
    Time polym. trim. trim. cat Me/ act × 106
    min cocat cat cat. mol % Tm(° C.) 1000 C g/molh Mw Mw/Mn
    Example 5 51 TIBA/CB 4 3 10 129.2 5 0.94 210000 1.5
    Comparative 6 TIBA/AB 5 1 10 134.5 — 23.1 — —
    Example 3
    Comparative 2 TIBA/CB 5 1 10 134.8 — 63.0 — —
    Example 4
    • INDUSTRIAL APPLICABILITY
  • The production process of the present invention has high industrial applicability as being capable of producing an ethylenic polymer having a low melting point economically.

Claims (3)

1. A process for producing an ethylenic polymer, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein
the catalytic component for olefin polymerization comprises a transition metal complex represented by the following general formula (1):
Figure US20120184693A1-20120719-C00008
wherein
M1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
A1 represents an atom of Group 16 of the Periodic Table of the Elements;
J1 represents an atom of Group 14 of the Periodic Table of the Elements;
Cp1 represents a group having a cyclopentadiene-type anionic skeleton;
X1, X2, R1, R2, R3 and R4 each independently represent
a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
R5 and R6 each independently represent
a hydrogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
of R1, R2, R3 and R4, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X1 and X2 may be bonded to each other to form a ring together with M1; and R5 and R6 may be bonded to each other to form a ring together with J1, and
the catalytic component for trimerization comprises a transition metal complex represented by the following general formula (2):

[Cp2-J2(R9)2—Ar]M2X3X4X5  (2)
wherein Cp1 represents a group having a cyclopentadiene-type anionic skeleton; M2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements; J2 represents a carbon atom; Ar represents an aryl group which may have a substituent; R9 represents a hydrocarbyl group which may have a substituent or a hydrogen atom, and
the two R9 groups may be the same as or different from each other and may be bonded to each other to form ring together with J2; and
X3, X4 and X5 each independently represent
a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20, and
of X3, X4 and X5, two groups may be bonded to each other to form a ring together with M2.
2. The process for producing an ethylenic polymer according to claim 1, wherein the catalytic component for trimerization comprises a transition metal complex in which Cp2 in the general formula (2) is η5-trimethylsilylcyclopentadienyl group.
3. A process for producing an ethylenic polymer, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtained by bringing a catalytic component for olefin polymerization, a catalytic component for trimerization and an activating co-catalytic component into contact with each other, wherein
the catalytic component for olefin polymerization comprises a transition metal complex represented by the following general formula (1):
Figure US20120184693A1-20120719-C00009
wherein
M1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
A1 represents an atom of Group 16 of the Periodic Table of the Elements;
J1 represents an atom of Group 14 of the Periodic Table of the Elements;
Cp1 represents a group having a cyclopentadiene-type anionic skeleton;
X1, X2, R1, R2, R3 and R4 each independently represent
a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
R5 and R6 each independently represent
a hydrogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
of R1, R2, R3 and R4, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X1 and X2 may be bonded to each other to form a ring together with M1; and R5 and R6 may be bonded to each other to form a ring together with J1, and
the catalytic component for trimerization comprises a transition metal complex represented by the following general formula (3):
Figure US20120184693A1-20120719-C00010
wherein
M3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
R10, R11, R12, R13 and R14 each independently represent a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
R15 and R16 each independently represent
a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
X6, X7 and X8 each independently represent
a hydrogen atom, a halogen atom,
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by —Si(R7)3, wherein the three R7 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R7 groups is 1 to 20, or
a disubstituted amino group represented by —N(R8)2, wherein the two R8 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R8 groups is 2 to 20;
of R10, R11, R12, R13 and R14, two groups bonded to two adjacent carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; X6, X7 and X8 may be bonded to each other to form a ring together with M3; and R15 and R16 may be bonded to each other to form a ring together with the silicon atom to which R15 and R16 are bonded.
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