US20120184431A1 - Transition metal complex, preparation method for said transition metal complex, trimerization catalyst, preparation method for 1-hexene, preparation method for ethylene polymer, substituted cyclopentadiene compound, and preparation method for said substituted cyclopentadiene compound - Google Patents

Transition metal complex, preparation method for said transition metal complex, trimerization catalyst, preparation method for 1-hexene, preparation method for ethylene polymer, substituted cyclopentadiene compound, and preparation method for said substituted cyclopentadiene compound Download PDF

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US20120184431A1
US20120184431A1 US13/498,980 US201013498980A US2012184431A1 US 20120184431 A1 US20120184431 A1 US 20120184431A1 US 201013498980 A US201013498980 A US 201013498980A US 2012184431 A1 US2012184431 A1 US 2012184431A1
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halogen atom
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Yasutoyo Kawashima
Takahiro Hino
Taichi Senda
Masaya TANIMOTO
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Sumitomo Chemical Co Ltd
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    • 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
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    • 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
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    • 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
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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 transition metal complex, a process for producing the transition metal complex, a trimerization catalyst, a process for producing 1-hexene, a process for producing an ethylenic polymer, a substituted cyclopentadiene compound and a process for producing the substituted cyclopentadiene compound.
  • ⁇ -olefin is an industrially important raw material monomer that is produced by the oligomerization of ethylene using a metal catalyst.
  • the oligomerization of ethylene usually gives ⁇ -olefin mixtures according to Shultz-Flory distribution. Therefore, the development of a catalyst system capable of selectively producing ⁇ -olefin is very important industrially.
  • PATENT DOCUMENT 1 has reported that a half-metallocene titanium complex represented by the formula (Cp-B(R) n Ar)TiR 1 3 works as a catalytic component for selective trimerization of ethylene in the presence of an activating co-catalytic component.
  • a half-metallocene titanium complex comprising cyclopentadiene bonded to a substituted aryl group via a carbon atom, such as [1-(1-methyl-1-(3,5-dimethylphenyl)ethyl)-3-trimethylsilylcyclopentadienyl]titanium trichloride, has been reported to work as an efficient ethylene trimerization catalyst under condition of 30° C. with MAO (methylaluminoxane) as an activating co-catalytic component (see e.g., NON-PATENT DOCUMENT 1).
  • MAO methylaluminoxane
  • An ethylenic copolymer having a main chain with ethylene units and an alkyl side chain e.g., an ethyl or butyl branch
  • linear low-density polyethylene has conventionally been produced by copolymerizing ethylene and ⁇ -olefin (e.g., 1-butene or 1-hexene) in the presence of an olefin polymerization catalyst.
  • an olefin polymerization catalyst obtainable by bringing dimethylsilylene(tert-butylamido)(tetramethylcyclopentadienyl)titanium dichloride as an olefin copolymerization catalyst, [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride as an ethylene trimerization catalyst, and MMAO as an activating co-catalytic component into contact with each other (see NON-PATENT DOCUMENTS 3 and 4).
  • NON-PATENT DOCUMENT 4 discloses that an ethylenic polymer having a low melting point is obtained by polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing rac-dimethylsilylenebis(2-methylbenz[e]indenyl)zirconium dichloride as an olefin copolymerization catalyst, [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium trichloride as an ethylene trimerization catalyst, and MMAO as an activating co-catalytic component into contact with each other.
  • an olefin polymerization catalyst obtainable by bringing rac-dimethylsilylenebis(2-methylbenz[e]indenyl)zirconium dichloride as an olefin copolymerization catalyst, [1-(1-methyl-1-phenylethyl)-cyclopentadienyl]titanium t
  • an object of the present invention is to provide a transition metal complex that serves as a catalytic component capable of efficiently and highly selectively producing 1-hexene through the trimerization reaction of ethylene even under high temperature conditions.
  • Another object of the present invention is to provide a process for economically producing an ethylenic polymer having a butyl branch even under high temperature conditions, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing the transition metal complex used as an ethylene trimerization catalyst, an olefin copolymerization catalyst and an activating co-catalytic component into contact with each other.
  • a 1st aspect of the present invention relates to 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; R 1 , R 2 , R 3 and R 4 each independently represent
  • a 2nd aspect of the present invention relates to a trimerization catalyst which is obtainable by contacting the above-mentioned transition metal complex with an activating co-catalytic component.
  • a 3rd aspect of the present invention relates to a process for producing 1-hexene using the trimerization catalyst.
  • a 4th 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 contacting
  • a catalytic component for olefin polymerization a catalytic component for trimerization comprising a transition metal complex represented by the following general formula (1), and an activating co-catalytic component:
  • M 1 represents a transition metal atom of Group 4 of the Periodic Table of the Elements; R 1 , R 2 , R 3 and R 4 each independently represent
  • a 5th aspect of the present invention relates to a process for producing the transition metal complex represented by the general formula (1) or a transition metal complex represented by the following general formula (1-2) or (1-3):
  • R 22 , R 23 and R 24 each independently represent a halogen atom, 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, or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, and at least one of R 22 , R 23 and R 24 is the alkyl group, the aryl group or the aralkyl group; and
  • R 25 , R 26 and R 27 each independently represent a halogen atom, an alkoxy group having 1 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, or an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, and at least one of R 25 , R 26 and R 27 is the alkoxy group, the aryloxy group or the aralkyloxy group.
  • a 6th aspect of the present invention relates to a substituted cyclopentadiene compound represented by general formula (6-1):
  • R 28 , R 29 , R 30 and R 31 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydrocarby
  • R 39 R 40 , R 41 and R 42 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydrocarbyl group
  • R 46 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarby
  • R 50 , R 51 , R 52 and R 53 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 12 ) 3 , wherein the three R 12 s each independently represent a hydrogen atom, a hydrocar
  • R 61 , R 62 , R 63 and R 64 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a flu
  • R 65 , R 66 , R 67 , R 68 an R 69 is methypheny, dimethypheny, trimethypheny, tetramethylphenyl, pentamethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, anthracene, chlorophenyl, dichlorophenyl, fluorophenyl or bis(trifluoromethyl)phenyl; each of R 70 and R 71 is a methyl group; and the moiety
  • R 72 , R 73 , R 74 and R 75 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydroch
  • R 83 , R 84 , R 85 and R 86 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a flu
  • a 7th aspect of the present invention relates to a process for producing the substituted cyclopentadiene compound represented by any of the general formulas (6-1) to (6-6).
  • the present invention can provide a transition metal complex that is suitable as a catalytic component capable of efficiently and highly selectively producing 1-hexene through the trimerization reaction of ethylene even under high temperature conditions.
  • the present invention can further provide a process for economically producing an ethylenic polymer having a butyl branch even under high temperature conditions, comprising polymerizing ethylene in the presence of an olefin polymerization catalyst obtainable by bringing the transition metal complex, which is used as an ethylene trimerization catalyst, an olefin copolymerization catalyst and an activating co-catalyst into contact with each other.
  • FIG. 1 graphically represents the time-dependent change of ethylene absorption in an embodiment of the present invention.
  • FIG. 2 graphically represents the time-dependent change of ethylene absorption in an embodiment of the present invention.
  • FIG. 3 graphically represents the time-dependent change of ethylene absorption in an embodiment of the present invention.
  • FIG. 4 graphically represents the time-dependent change of ethylene absorption in an embodiment of the present invention.
  • FIG. 5 graphically represents the time-dependent change of ethylene absorption in an embodiment of the present invention.
  • the term “polymerization” encompasses not only homopolymerization but also copolymerization.
  • the term “substituent” encompasses a halogen atom constituting a compound or a group.
  • substituted cyclopentadiene compounds represented by general formulae (6) and (6-1) to (6-6) respectively have isomers differing in the double bond position of each cyclopentadienyl ring.
  • the substituted cyclopentadienyl compounds refer to any of them or a mixture of them.
  • M 1 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 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , X 1 , X 2 and X 3 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.
  • a preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof 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.
  • a preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof include 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 can specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof can 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.
  • a preferable alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and more preferable examples thereof 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.
  • a preferable alkoxy group is an alkoxy group having 2 to 10 carbon atoms, and more preferable examples thereof include ethoxy and ten-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 2 to 20, more preferably in the range of 2 to 10.
  • a preferable aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and more preferable examples thereof 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.
  • a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof include 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 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 12 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., phenyl group); or a halogenated hydrocarbyl
  • the total number of the carbon atoms in the these three R 12 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 of these groups 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 of these groups with a halogen atom; and trisubstituted silyl group having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, trieth
  • 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 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 groups is 2 to 20
  • the R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 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 13 groups may be bonded to each other to form a ring together with the nitrogen atom to which these two R 13 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 1 , R 2 , R 3 and R 4 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
  • R 10 and R 11 may be bonded to each other to form a ring together with the silicon atom to which R 10 and are bonded
  • R 5 , R 6 , R 7 , R 8 and R 9 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 is a saturated or unsaturated hydrocarbyl ring substituted with a hydrocarbyl group having 1 to 20 carbon atoms, a saturated or unsaturated silahydrocarbyl ring substituted by a hydrocarbyl group having 1 to 20 carbon atoms, etc.
  • cyclopropane examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexane, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopropane and silacyclohexane rings.
  • At least one of R 1 , R 2 , R 3 and R 4 is a substituent other than hydrogen and is 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.
  • R 1 , R 2 , R 3 and R 4 are those that can provide a cyclopentadienyl substructure represented by substructural formula (15):
  • R 1 , R 2 , R 3 and R 4 are as defined above, and at least one thereof is a substituent other than hydrogen.
  • methylcyclopentadienyl ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl and octahydrofluorenyl.
  • the preferable cyclopentadienyl substructures are tetramethylcyclopentadienyl, etc.
  • R 5 , R 6 , R 7 , R 8 and R 9 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 the preferable combination of the moieties represented by R 5 , R 6 , R 7 , R 8 and R 9 can include those that can provide the following substructures represented by substructural formula (16):
  • R 5 , R 6 , R 7 , R 8 and R 9 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, bis(trifluoromethyl)phenyl and methoxyphenyl.
  • the preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, etc.
  • R 10 and R 11 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 the moieties represented by R 10 and R 11 can include those that can provide the following substructures represented by substructural formula (17):
  • R 10 and R 11 are as defined above:
  • Preferable examples thereof can include a substructure represented by the substructural formula (17), wherein
  • R 10 is a methyl group
  • R 11 is an alkyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent; or R 10 and R 11 are the same and represent an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
  • the substructure can be dimethylsilylene, diethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene, etc.
  • transition metal complex of the formula (1) can include transition metal complexes, wherein R 6 and R 8 are
  • R 10 and R 11 are an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
  • transition metal complex (1) can include the following complexes:
  • titanium chloride complexes such as [1-dimethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-3-methylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadie
  • examples of the transition metal complex (1) also include: transition metal chloride complexes such as zirconium chloride complexes in which “titanium” in the complexes exemplified above is replaced with “zirconium”, and hafnium chloride complexes in which “titanium” is replaced with “hafnium”; titanium halide complexes such as titanium fluoride complexes in which “chloride” in the complexes are replaced with “fluoride”, titanium bromide complexes in which “chloride” is replaced with “bromide” and titanium iodide complexes in which “chloride” is replaced with “iodide”; titanium hydride complexes in which “chloride” is replaced with “hydride”; alkylated titanium complexes such as a methylated titanium complex in which “chloride” is replaced with “methyl”; arylated titanium complexes such as a phenylated titanium complex in which “chloride” is replaced with “
  • transition metal complex of formula (1) include [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-cyclotetramethylene(phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium t
  • More preferable examples thereof include [1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride and [1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride.
  • the transition metal complex (1) can be produced by, for example, a production process comprising the steps of:
  • substituted cyclopentadiene compound (6) a substituted cyclopentadiene compound represented by a formula (6) (hereinafter, referred to as a “substituted cyclopentadiene compound (6)”) with a base in the presence of an amine compound:
  • X 12 independently at each occurrence 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 12 ) 3 , wherein the three R 12 groups
  • the step of reacting a substituted cyclopentadiene compound (6) with a base in the presence of an amine compound may be referred to as a “1st reaction step”, and the step of reacting the reaction product of the substituted cyclopentadiene compound (6) and the base with a transition metal compound (7) may be referred to as a “2nd reaction step”.
  • Isomers of the substituted cyclopentadiene compound (6), differing in the double bond position of the cyclopentadiene ring include the following structural isomers:
  • the compound represented by the general formula (6) has isomers differing in the double bond position of each cyclopentadienyl ring. In the present invention, it represents any of them or a mixture of them.
  • the substituent X 12 is as defined above, and specific examples thereof can include the same as those exemplified for X 1 , X 2 and X 3 .
  • transition metal compound (7) examples include: titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide; titanium amidoes such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium and tetrakis(diethylamino)titanium; and titanium alkoxides titanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and trichloroisopropoxytitanium.
  • titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide
  • titanium amidoes such as tetrakis(di
  • examples of the transition metal compound (7) include compounds in which “titanium” in any of these compounds is replaced with “zirconium” or “hafnium”. Of them, a preferable transition metal compound (7) is titanium tetrachloride.
  • Examples of the base reacted with the substituted cyclopentadiene compound (6) in the 1st reaction step include organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium.
  • organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium.
  • the amount of the base used may be in the range of 0.5 to 5 moles per one mole of the substituted cyclopentadienyl compound (6).
  • an amine compound is used together with the organic alkali metal compound.
  • an amine compound include: primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine; secondary amine compounds such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine; and tertiary amine compounds such as trimethylamine, triethylamine, tri-n-propyl
  • the reaction of the substituted cyclopentadiene compound (6) with the base is preferably performed in the presence of a solvent.
  • the solvent when used, the substituted cyclopentadiene compound (6) and the base are reacted in the solvent and then a transition metal compound (7) can be added into this reaction mixture to thereby further react the transition metal compound (7) with the reaction product of the substituted cyclopentadiene compound (6) and the base.
  • Solids may be deposited in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (6) and the base.
  • the solvent may be further added until the deposited solid is dissolved; or the deposited solid may be temporarily separated by filtration or the like, and the solvent may be added to the separated solid for dissolution or suspension, followed by the addition of a transition metal compound (7).
  • the substituted cyclopentadiene compound (6), the base and the transition metal compound (7) can also be added simultaneously to the solvent to thereby perform the 1st reaction step and the 2nd reaction step almost simultaneously.
  • the solvent used in the 1st reaction step or in the 1st and 2nd reaction steps is an inert solvent that does not significantly hinder the progress of the reaction associated with these steps.
  • aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; and halogenic solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents can be used alone or as a mixture of two or more thereof
  • the amount of the transition metal compound (7) used is preferably in the range of 0.5 to 3 moles, more preferably in the range of 0.7 to 1.5 moles, per one mole of the substituted cyclopentadiene compound (6).
  • the reaction temperature in the 1st and 2nd reaction steps needs only to be a temperature not less than ⁇ 100° C. and not more than the boiling point of the solvent and is preferably in the range of ⁇ 80 to 100° C.
  • the produced transition metal complex (1) can be taken out by various purification methods known in the art.
  • the transition metal complex (1) of interest can be obtained by a method in which after the 1st and 2nd reaction steps, the formed precipitates are filtered off, and the filtrate is concentrated to deposit a transition metal complex, which is then collected by filtration.
  • the transition metal complex (1-2) can be produced, for example, by reacting a transition metal halide complex represented by general formula (1-1):
  • R 20 represents 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, or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or an alkaline earth metal compound represented by a formula (9):
  • R 21 represents 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, or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent
  • X 16 represents a halogen atom
  • r is 1 or 2
  • the total sum of r and s is 2.
  • transition metal complex (1-2) examples include alkylated titanium, arylated titanium and aralkylated titanium complexes.
  • the substituents R 22 , R 23 and R 24 are as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • transition metal halide complex (1-1) examples include titanium chloride, titanium fluoride, titanium bromide and titanium iodide complexes.
  • the substituents X 13 , X 14 and X 15 are as defined above, and specific examples thereof can include the same as those exemplified for X 1 , X 2 and X 3 .
  • M 6 represents an alkali metal of the Periodic Table of the Elements, and examples thereof include lithium, sodium and potassium atoms. Among them, lithium and sodium atoms are preferable, and a lithium atom is particularly preferable.
  • the substituent R 20 is as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • M 7 represents an alkaline earth metal of the Periodic Table of the Elements, and examples thereof include magnesium, calcium and strontium atoms. Among them, a magnesium atom is preferable.
  • the substituent R 21 is as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • the substituent X 16 is as defined above, and specific examples thereof can include the same as those exemplified for X 1 , X 2 and X 3 .
  • r is 1 or 2
  • the total sum of r and s is 2.
  • alkali metal compound (8) examples include: alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, neopentyllithium, amyllithium, n-hexyllithium, n-octyllithium, n-decyllithium, n-dodecyllithium, n-pentadecyllithium and n-eicosyllithium;
  • alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, neopentyllithium,
  • aralkyllithiums such as benzyllithium, (2-methylphenyl)methyllithium, (3-methylphenyl)methyllithium, (4-methylphenyl)methyllithium, (2,3-dimethylphenyl)methyllithium, (2,4-dimethylphenyl)methyllithium, (2,5-dimethylphenyl)methyllithium, (2,6-dimethylphenyl)methyllithium, (3,4-dimethylphenyl)methyllithium, (2,3,4-trimethylphenyl)methyllithium, (2,3,5-trimethylphenyl)methyllithium, (2,3,6-trimethylphenyl)methyllithium, trimethylphenyl)methyllithium, (2,4,6-trimethylphenyl)methyllithium, tetramethylphenyl)methyllithium, (2,3,4,6-tetramethylphenyl)methyllithium, (2,3,5,6-tetramethylphenyl)methyllithium, (pentamethylphenyl)methyl
  • aryllithiums such as phenyllithium, 3-tolyllithium, 4-tolyllithium, 2,3-xylyllithium, 2,5-xylyllithium, 2,6-xylyllithium, 3,4-xylyllithium, 3,5-xylyllithium, 2,3,4-trimethylphenyllithium, 2,3,5-trimethylphenyllithium, 2,3,6-trimethylphenyllithium, 2,4,6-trimethylphenyllithium, 3,4,5-trimethylphenyllithium, 2,3,4,5-tetramethylphenyllithium, 2,3,4,6-tetramethylphenyllithium, 2,3,5,6-tetramethylphenyllithium, pentamethylphenyllithium, ethylphenyllithium, n-propylphenyllithium, isopropylphenyllithium, n-butylphenyllithium, sec-butylphenyllithium, tert-buty
  • the amount of the alkali metal compound (8) used is usually in the range of 2- to 10-fold by mol, preferably in the range of 1- to 3-fold by mol, with respect to the transition metal halide complex (1-1).
  • alkaline earth metal compound (9) examples include: dialkylmagnesiums and asymmetric dialkylmagnesiums such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, di-tert-butylmagnesium, di-n-pentylmagnesium, di-neopentylmagnesium, diamylmagnesium, hexylmagnesium, di-n-octylmagnesium, di-n-decylmagnesium, di-n-dodecylmagnesium, di-n-pentadecylmagnesium and di-n-eicosylmagnesium;
  • diaralkylmagnesiums and asymmetric diaralkylmagnesiums such as dibenzylmagnesium, di-(2-methylphenyl)methylmagnesium, di-(3-methylphenyl)methylmagnesium, di-(4-methylphenyl)methylmagnesium, di-(2,3-dimethylphenyl)methylmagnesium, di-(2,4-dimethylphenyl)methylmagnesium, di-(2,5-dimethylphenyl)methylmagnesium, di-(2,6-dimethylphenyl)methylmagnesium, di-(3,4-dimethylphenyl)methylmagnesium, di-(2,3,4-trimethylphenyl)methylmagnesium, di-(2,3,5-trimethylphenyl)methylmagnesium, di-(2,3,6-trimethylphenyl)methylmagnesium, di-(3,4,5-trimethylphenyl)methylmagnesium, di-(2,4,6-trimethylphenyl)methylmagnesium
  • diarylmagnesiums and asymmetric diarylmagnesiums such as diphenylmagnesium, di-2-tolylmagnesium, di-3-tolylmagnesium, di-4-tolylmagnesium, di-2,3-xylylmagnesium, di-2,4-xylylmagnesium, di-2,5-xylylmagnesium, di-2,6-xylylmagnesium, di-3,4-xylylmagnesium, di-3,5-xylylmagnesium, di-2,3,4-trimethylphenylmagnesium, di-2,3,5-trimethylphenylmagnesium, di-2,3,6-trimethylphenylmagnesium, di-2,4,6-trimethylphenylmagnesium, di-3,4,5-trimethylphenylmagnesium, di-2,3,4,5-tetramethylphenylmagnesium, di-2,3,4,6-tetramethylphenylmagnesium, di-2,3,5,6-tetramethyl
  • asymmetric organic magnesium compounds such as alkylaralkylmagnesiums, alkylarylmagnesiums and aralkylarylmagnesiums;
  • alkylmagnesium chlorides such as methylmagnesium chloride, ethylmagnesium chloride, n-propylmagnesium chloride, isopropylmagnesium chloride, n-butylmagnesium chloride, sec-butylmagnesium chloride, tert-butylmagnesium chloride, n-pentylmagnesium chloride, neopentylmagnesium chloride, amylmagnesium chloride, n-hexylmagnesium chloride, n-octylmagnesium chloride, n-decylmagnesium chloride, n-dodecylmagnesium chloride, n-pentadecylmagnesium chloride and n-eicosylmagnesium chloride;
  • aralkylmagnesium chlorides such as benzylmagnesium chloride, (2-methylphenyl)methylmagnesium chloride, (3-methylphenyl)methylmagnesium chloride, (4-methylphenyl)methylmagnesium chloride, (2,3-dimethylphenyl)methylmagnesium chloride, (2,4-dimethylphenyl)methylmagnesium chloride, (2,5-dimethylphenyl)methylmagnesium chloride, (2,6-dimethylphenyl)methylmagnesium chloride, (3,4-dimethylphenyl)methylmagnesium chloride, (2,3,4-trimethylphenyl)methylmagnesium chloride, (2,3,5-trimethylphenyl)methylmagnesium chloride, (2,3,6-trimethylphenyl)methylmagnesium chloride, (3,4,5-trimethylphenyl)methylmagnesium chloride, (2,4,6-trimethylphenyl)methylmagnesium chloride, (2,3,4,5-tetramethylpheny
  • arylmagnesium chlorides such as phenylmagnesium chloride, 2-tolylmagnesium chloride, 3-tolylmagnesium chloride, 4-tolylmagnesium chloride, 2,3-xylylmagnesium chloride, 2,4-xylylmagnesium chloride, 2,5-xylylmagnesium chloride, 2,6-xylylmagnesium chloride, 3,4-xylylmagnesium chloride, 3,5-xylylmagnesium chloride, 2,3,4-trimethylphenylmagnesium chloride, 2,3,5-trimethylphenylmagnesium chloride, 2,3,6-trimethylphenylmagnesium chloride, 2,4,6-trimethylphenylmagnesium chloride, 3,4,5-trimethylphenylmagnesium chloride, 2,3,4,5-tetramethylphenylmagnesium chloride, 2,3,4,6-tetramethylphenylmagnesium chloride, 2,3,5,6-tetramethylphenylmagnesium chloride,
  • the amount of the alkaline earth metal compound (9) used is usually in the range of 1- to 10-fold by mol, preferably in the range of 1- to 3-fold by mol, with respect to the transition metal halide complex (1-1).
  • the reaction method is not particularly limited, and the reaction is usually preferably performed by adding the organic alkali metal or alkaline earth metal compound to the transition metal halide complex (1-1) in the presence of a solvent in an inert atmosphere of nitrogen, argon, or the like.
  • Examples of the solvent for the reaction can include: aliphatic hydrocarbyl solvents such as pentane, hexane, cyclohexane, heptane and octane; aromatic hydrocarbyl solvents such as benzene, toluene, xylene, mesitylene and ethylbenzene; halogenated hydrocarbyl solvents such as chloroform, methylene dichloride, monochlorobenzene and dichlorobenzene; and ethers such as diethyl ether, dibutyl ether, methyl-t-butyl ether and tetrahydrofuran. These solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually in the range of 1- to 200-fold by weight, preferably in the range of 3- to 30-fold by weight, with respect to the transition metal halide complex (1-1).
  • aromatic hydrocarbyl solvents such as benzene, toluene
  • the temperature of the reaction is usually ⁇ 100° C. to the boiling point of the solvent, preferably ⁇ 80° C. to 30° C.
  • the reaction time is not particularly limited. After the completion of the reaction, for example, insoluble matter is filtered off, and the filtrate is then concentrated to obtain a crystal, which can then be collected by filtration to obtain the transition metal complex (1-2) of interest.
  • the transition metal complex (1-3) can be produced, for example, by reacting a transition metal halide complex represented by general formula (1-1):
  • M 6 and R 20 are as defined above, or an alkaline earth metal compound represented by formula (11):
  • M 7 , R 21 , X 16 , r and s are as defined above.
  • transition metal complex (1-3) examples include titanium alkoxide, titanium aryloxide and titanium aralkyloxide complexes.
  • the substituents R 25 , R 26 and R 27 are as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • transition metal halide complex (1-1) examples include titanium chloride, titanium fluoride, titanium bromide and titanium iodide complexes.
  • the substituents X 13 , X 14 and X 15 are as defined above, and specific examples thereof can include the same as those exemplified for X 1 , X 2 and X 3 .
  • M 6 represents an alkali metal of the Periodic Table of the Elements, and examples thereof include lithium, sodium and potassium atoms. Among them, lithium and sodium atoms are preferable, and a lithium atom is particularly preferable.
  • the substituent R 20 is as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • M 7 represents an alkaline earth metal of the Periodic Table of the Elements, and examples thereof include magnesium, calcium and strontium atoms. Among them, a magnesium atom is preferable.
  • the substituent R 21 is as defined above, and specific examples thereof can include the same as those exemplified for R 1 .
  • the substituent X 16 is as defined above, and specific examples thereof can include the same as those exemplified for X 1 , X 2 and X 3 .
  • r is 1 or 2
  • the total sum of r and s is 2.
  • the transition metal complex (1-3) can be produced by a process in which the alkali metal compound (10) is allowed to act on the transition metal complex (1-1) (hereinafter, referred to as process A-1) or by a process in which the alkaline earth metal compound (11) is allowed to act thereon (hereinafter, referred to as process A-2).
  • the transition metal complex (1-3) can also be produced by a process in which an alcohol compound is allowed to act on the transition metal complex (1-1) in the presence of a base (hereinafter, referred to as process B).
  • alkali metal compound represented by the general formula (10) examples include: sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium isopropoxide, sodium n-butoxide, sodium sec-butoxide, sodium tert-butoxide, sodium n-pentoxide, sodium neopentoxide, sodium methoxyethoxide, sodium ethoxyethoxide, sodium benzyloxide, sodium 1-phenylethoxide, and alkali metal alkoxides derived from monools, in which sodium is replaced with lithium or potassium in these compounds;
  • alkali metal compound (10) A commercially available product or the like can be used as the alkali metal compound (10).
  • the alkali metal compound (10) can also be produced in the system, for use, through the reaction between an alcohol compound and an alkali metal compound.
  • alkali metal compound used in the production of the alkali metal compound (10) in the system examples include: alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, neopentyllithium, amyllithium, n-hexyllithium, n-octyllithium, n-decyllithium, n-dodecyllithium, n-pentadecyllithium and n-eicosyllithium;
  • alkyllithiums such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-penty
  • aralkyllithiums such as benzyllithium, (2-methylphenyl)methyllithium, (3-methylphenyl)methyllithium, (4-methylphenyl)methyllithium, (2,3-dimethylphenyl)methyllithium, (2,4-dimethylphenyl)methyllithium, (2,5-dimethylphenyl)methyllithium, (2,6-dimethylphenyl)methyllithium, (3,4-dimethylphenyl)methyllithium, (2,3,4-trimethylphenyl)methyllithium, (2,3,5-trimethylphenyl)methyllithium, (2,3,6-trimethylphenyl)methyllithium, (3,4,5-trimethylphenyl)methyllithium, (2,4,6-trimethylphenyl)methyllithium, (2,3,4,5-tetramethylphenyl)methyllithium, (2,3,4,6-tetramethylphenyl)methyllithium, (2,3,5,6-tetramethylphenyl)methyllithium, (p
  • aryllithiums such as phenyllithium, 2-tolyllithium, 3-tolyllithium, 4-tolyllithium, 2,3-xylyllithium, 2,4-xylyllithium, 2,5-xylyllithium, 2,6-xylyllithium, 3,4-xylyllithium, 3,5-xylyllithium, 2,3,4-trimethylphenyllithium, 2,3,5-trimethylphenyllithium, 2,3,6-trimethylphenyllithium, 2,4,6-trimethylphenyllithium, 3,4,5-trimethylphenyllithium, 2,3,4,5-tetramethylphenyllithium, 2,3,4,6-tetramethylphenyllithium, 2,3,5,6-tetramethylphenyllithium, pentamethylphenyllithium, ethylphenyllithium, n-propylphenyllithium, isopropylphenyllithium, n-butylphenyllithium,
  • examples of the alcohol compound used include monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzyl alcohol, 1-phenylethanol, and so on.
  • monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzyl alcohol, 1-phenylethanol, and so on.
  • alkaline earth metal compound represented by the general formula (11) examples include: alkaline earth metal alkoxides derived from monools, such as magnesium dimethoxide, magnesium diethoxide, magnesium di-n-propoxide, magnesium diisopropoxide, magnesium di-n-butoxide, magnesium di-sec-butoxide, magnesium di-tert-butoxide, magnesium di-n-pentoxide, magnesium dineopentoxide, magnesium dimethoxyethoxide, magnesium diethoxyethoxide, magnesium dibenzyloxide, and magnesium di-1-phenylethoxide, and those obtained by changing magnesium in these compounds to calcium, strontium or barium; and alkaline earth metal alkoxides derived from diols, such as magnesium ethylenedioxide, magnesium methylethylenedioxide, magnesium 1,2-dimethylethylenedioxide, magnesium tetramethylethylenedioxide, magnesium phenylethylenedioxide, magnesium 1,2-diphenylethylenedi
  • alkaline earth metal compound (11) A commercially available product or the like can be used as the alkaline earth metal compound (11).
  • the alkaline earth metal compound (11) can also be produced in the system, for use, through the reaction between an alcohol compound and an alkaline earth metal compound.
  • Examples of such an alkaline earth metal compound used in the production of the alkaline earth alkoxides in the system include Grignard reagents such as methylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, phenylmagnesium bromide and benzylmagnesium bromide. Preferable examples thereof include methylmagnesium chloride and methylmagnesium bromide.
  • examples of the alcohol compound used include: monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzyl alcohol and 1-phenylethanol; and dials such as ethylene glycol, propylene glycol, 2,3-butanediol, tetramethylethylene glycol, phenylethylene glycol, hydrobenzoin, tetraphenylethylene glycol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, 1,3-propanediol, 2,4-pentanediol, 1,3-diphenyl-1,3-propanediol and tartaric acid.
  • Examples of the alcohol compound used in the method B include monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzyl alcohol and 1-phenylethanol.
  • monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, neopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, phenol, benzyl alcohol and 1-phenylethanol.
  • the base examples include: inorganic bases such as alkali metal hydroxides and alkali metal carbonates; and organic bases such as amine compounds, and preferably include amine compounds.
  • examples of the amine compounds include, but not particularly limited to:
  • primary amines such as aniline, chloroaniline, bromoaniline, fluoroaniline, toluidine, anisidine, naphthylamine, benzylamine, propylamine, butylamine and pentylamine
  • secondary amines such as N-methylaniline, N-ethylaniline, diphenylamine, N-methylchloroaniline, N-methylbromoaniline, N-methylfluoroaniline, pyrrolidine, morpholine and piperidine
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-dimethylchloroaniline, N,N-dimethylbromoaniline, N,N-dimethylfluoroaniline, N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine, 1,4-diazabicyclo[2,2,2]octan
  • the reaction process is not particularly limited, and the reaction is preferably performed by reacting the transition metal complex (1-1) with the alkali metal compound (10) (process A-1) or the alkaline earth metal compound (11) (process A-2) or with the alcohol compound in the presence of a base (process B), in the presence of a solvent in an inert atmosphere of nitrogen, argon, or the like.
  • the amount of the alkali metal compound (10) used with respect to the transition metal complex (1-1) is usually approximately 0.5- to 15-fold by mol, preferably approximately 0.8- to 3-fold by mol.
  • the amount of the alkaline earth metal compound (11) used with respect to the transition metal complex (1-1) is usually approximately 0.3- to 10-fold by mol, preferably approximately 0.5- to 2-fold by mol.
  • the amount of the alcohol compound used with respect to the transition metal complex (1-1) is usually approximately 0.5- to 10-fold by mol, preferably approximately 0.8- to 3-fold by mol, and the amount of the base used with respect to the transition metal complex (1-1) is usually approximately 0.5- to 5-fold by mol, preferably approximately 0.8- to 3-fold by mol.
  • Examples of the solvent that can be used in the reactions include, but not particularly limited to: aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbyl solvents such as benzene, toluene, xylene and mesitylene; halogenated aliphatic hydrocarbyl solvents such as dichloromethane, chloroform and dichloroethane; halogenated aromatic hydrocarbyl solvents such as monochlorobenzene and dichlorobenzene; ethers such as diethyl ether, dibutyl ether, methyl t-butyl ether and tetrahydrofuran; alcohols correspond to the alkali metal compound (10); and mixtures thereof.
  • the amount thereof used is usually 1- to 200-fold by weight, preferably approximately 3- to 30-fold by weight, with respect to the transition metal complex (1-1) in each of the processes A-1, A-2 and B
  • the reaction temperature is usually ⁇ 100° C. to the boiling point of the solvent, preferably approximately ⁇ 80 to 30° C.
  • transition metal complex (1-3) can be purified, if necessary, by a usual method such as recrystallization and sublimation.
  • the substituents R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 R 37 and R 38 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-1) can include the following compounds:
  • the substituted cyclopentadiene compounds exemplified above may have isomers differing in the double bond position of the cyclopentadiene ring. A mixture of these isomers may also be used in the present invention.
  • Examples of the substituted cyclopentadiene compound (6-2) can include the following compounds:
  • the substituted cyclopentadiene compounds exemplified above may have isomers differing in the double bond position of the cyclopentadiene ring. A mixture of these isomers may also be used in the present invention.
  • the substituents R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-3) can include the following compounds:
  • the substituted cyclopentadiene compounds exemplified above may have isomers differing in the double bond position of the cyclopentadiene ring. A mixture of these isomers may also be used in the present invention.
  • the substituents R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 and R 71 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-4) can include the following compounds:
  • the substituted cyclopentadiene compounds exemplified above may have isomers differing in the double bond position of the cyclopentadiene ring. A mixture of these isomers may also be used in the present invention.
  • R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 and R 82 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-5) can include the following compounds:
  • the substituted cyclopentadiene compounds exemplified above may have isomers differing in the double bond position of the cyclopentadiene ring. A mixture of these isomers may also be used in the present invention.
  • R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 89 , R 90 , R 91 , R 92 and R 93 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-6) can include the following compounds:
  • the substituted cyclopentadiene compounds represented by the general formulas (6-1) to (6-6) can be produced, for example, by the steps of reacting substituted cyclopentadiene compounds represented by general formulas (12-1) to (12-6) with a base in the presence of an amine compound;
  • R 28 , R 29 , R 30 and R 31 are as defined above, and the moiety
  • R 39 , R 40 , R 41 and R 42 are as defined above, and the moiety
  • R 49 , R 50 , R 51 and R 52 are as defined above, and the moiety
  • R 61 , R 62 , R 63 and R 64 are as defined above, and the moiety
  • R 72 , R 73 , R 74 and R 75 are as defined above, and the moiety
  • R 83 , R 84 , R 85 and R 86 are as defined above, and the moiety
  • Examples of the substituted cyclopentadiene compounds (12-1), (12-2), (12-4) and (12-5) can include the following compounds:
  • methylcyclopentadiene 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,3,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene, 1,3,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopenta
  • Examples of the substituted cyclopentadiene compound (12-3) can include the following compounds:
  • tetrahydroindene 2-methyltetrahydroindene, 3-methyltetrahydroindene, 2,3-dimethyltetrahydroindene, 2-ethyltetrahydroindene, 2-n-propyltetrahydroindene, 2-isopropyltetrahydroindene, 2-n-butyltetrahydroindene, 2-sec-butyltetrahydroindene, 2-tert-butyltetrahydroindene, 2-n-pentyltetrahydroindene, 2-neopentyltetrahydroindene, 2-amyltetrahydroindene, 2-n-hexyltetrahydroindene, 2-cyclohexyltetrahydroindene, 2-n-octyltetrahydroindene, 2-n-decyltetrahydroindene, 2-phenyltetrahydr
  • Examples of the substituted cyclopentadiene compound (12-6) can include the following compounds:
  • methylcyclopentadiene 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,3,4-trimethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene, 1,3,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene, neopentylcyclopentadiene, n-hexylcyclopentadiene
  • the silicon halide compounds represented by the general formulas (13-1) to (13-6) are as follows:
  • R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 are as defined above, and X 17 is a halogen atom;
  • R 43 , R 44 , R 45 , e, R 47 , R 48 and R 49 are as defined above, and X 18 is a halogen atom;
  • R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 are as defined above, and X 19 is a halogen atom;
  • R 65 , R 66 , R 67 , R 68 , R 69 , R 70 and R 71 are as defined above, and X 20 is a halogen atom;
  • R 76 , R 77 , R 78 , R 79 , R 80 , R 81 and R 82 are as defined above, and X 21 is a halogen atom;
  • R 87 , R 88 , R 89 , R 90 , R 91 , R 92 and R 93 are as defined above, and X 22 is a halogen atom.
  • Examples of the silicon halide compound (13-1) can include the following compounds:
  • Examples of the silicon halide compound (13-2) can include the following compounds:
  • chlorotriphenylsilane chloro(2-methylphenyl)diphenylsilane, chloro(3-methylphenyl)diphenylsilane, chloro(4-methylphenyl)diphenylsilane, chloro(2,3-dimethylphenyl)diphenylsilane, chloro(2,4-dimethylphenyl)diphenylsilane, chloro(2,5-dimethylphenyl)diphenylsilane, chloro(2,6-dimethylphenyl)diphenylsilane, chloro(3,4-dimethylphenyl)diphenylsilane, chloro(3,5-dimethylphenyl)diphenylsilane, chloro(3,6-dimethylphenyl)diphenylsilane, chloro(2,3,4-trimethylphenyl)diphenylsilane, chloro(2,3,5-trimethylphenyl)diphenylsilane, chloro(
  • Examples of the silicon halide compound (13-3) can include the following compounds:
  • chlorodimethylphenylsilane chloroethylmethylphenylsilane, chlorodiethylphenylsilane, chloromethyl(n-propyl)phenylsilane, chloromethyl(isopropyl)phenylsilane, chloro(n-butyl)methylphenylsilane, chloro(sec-butyl)methylphenylsilane, chloro(tert-butyl)methylphenylsilane, chloromethyl(n-pentyl)phenylsilane, chloromethyl(neopentyl)phenylsilane, amylchloromethylphenylsilane, chloro(n-hexyl)methylphenylsilane, chlorocyclohexylmethylphenylsilane, chloromethyl(n-octyl)phenylsilane, chloro(n-decyl)methylphenylsilane, chloro(n-dodec
  • chlorodimethyl(3-methylphenyl)silane chlorodimethyl(4-methylphenyl)silane, chlorodimethyl(3,5-dimethylphenyl)silane, chlorodimethyl(4-n-butylphenyl)silane, chlorodimethyl(4-phenylphenyl)silane, chlorodimethyl(4-methoxyphenyl)silane, chlorodimethyl(4-phenoxyphenyl)silane, chlorodimethyl(4-trimethylsilylphenyl)silane, chlorodimethyl(4-dimethylaminophenyl)silane, chlorodimethyl(4-benzyloxyphenyl)silane,
  • chloromethyldiphenylsilane chloromethyl(2-methylphenyl)phenylsilane, chloromethyl(3-methylphenyl)phenylsilane, chloromethyl(4-methylphenyl)phenylsilane, chloromethyl(2,3-dimethylphenyl)phenylsilane, chloromethyl(2,4-dimethylphenyl)phenylsilane, chloromethyl(2,5-dimethylphenyl)phenylsilane, chloromethyl(2,6-dimethylphenyl)phenylsilane, chloromethyl(3,4-dimethylphenyl)phenylsilane, chloromethyl(3,5-dimethylphenyl)phenylsilane, chloromethyl(3,6-dimethylphenyl)phenylsilane, chloromethyl(2,3,4-trimethylphenyl)phenylsilane, chloromethyl(2,3,5-trimethylphenyl)phenylsilane, chloro
  • chlorotriphenylsilane chloro(2-methylphenyl)diphenylsilane, chloro(3-methylphenyl)diphenylsilane, chloro(4-methylphenyl)diphenylsilane, chloro(2,3-dimethylphenyl)diphenylsilane, chloro(2,4-dimethylphenyl)diphenylsilane, chloro(2,5-dimethylphenyl)diphenylsilane, chloro(2,6-dimethylphenyl)diphenylsilane, chloro(3,4-dimethylphenyl)diphenylsilane, chloro(3,5-dimethylphenyl)diphenylsilane, chloro(3,6-dimethylphenyl)diphenylsilane, chloro(2,3,4-trimethylphenyl)diphenylsilane, chloro(2,3,5-trimethylphenyl)diphenylsilane, chloro(
  • Examples of the silicon halide compound (13-4) can include the following compounds:
  • Examples of the silicon halide compound (13-5) can include the following compounds:
  • Examples of the silicon halide compound (13-6) can include the following compounds:
  • chlorodimethylphenylsilane bromodimethylphenylsilane, fluorodimethylphenylsilane and iododimethylphenylsilane.
  • Examples of the base to be reacted with the substituted cyclopentadiene compounds (12-1) to (12-6) include: alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; alkaline earth metal hydrides such as calcium hydride; and organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium.
  • alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride
  • alkaline earth metal hydrides such as calcium hydride
  • organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-
  • the amount thereof used is usually in the range of 0.5- to 3-fold by mol, preferably in the range of 0.9- to 2-fold by mol, with respect to the substituted cyclopentadiene compound.
  • a usual commercially available mineral oil-containing product can be used directly as sodium hydride or potassium hydride. Of course, prior to the usage, the mineral oil may be removed, by washing with a hydrocarbyl solvent such as hexane.
  • Examples of the amine compound include: Primary amines including primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline, dibromoaniline, difluoroaniline, trichloroaniline, tribromoaniline, trifluoroaniline, tetrachloroaniline, tetrabromoaniline, tetrafluoroaniline, pentachloroaniline, pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline, phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline, isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline, t-butoxyaniline, phenoxyaniline, methylaniline, ethylaniline, n
  • secondary amines such as N-methylaniline, N-ethylaniline, diphenylamine, N-methylchloroaniline, N-methylbromoaniline, N-methylfluoroaniline, N-methylanisidine, N-methylmethylaniline, N-methylethylaniline, N-methyl-n-propylaniline, N-methylisopropylaniline, diethylamine, dipropylamine, diisopropylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, morpholine, piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2-methylaminopyridine, 3-methylaminopyridine and 4-methylaminopyridine; and
  • tertiary amines such as N,N-dimethylaniline, N,N-dimethylchloroaniline, N,N-dimethylbromoaniline, N,N-dimethylfluoroaniline, N,N-dimethylanisidine, N-methylmethylaniline, N,N-dimethylethylaniline, N,N-dimethyl-n-propylaniline, N,N-dimethylisopropylaniline, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-
  • the amount thereof used is usually in the range of 0.001- to 2-fold by mol, preferably in the range of 0.01- to 0.5-fold by mol, with respect to the metal hydride.
  • the reaction is usually performed in a solvent inert to the reaction.
  • aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene.
  • aromatic hydrocarbyl solvents such as benzene, toluene and xylene
  • aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane
  • any of the substituted cyclopentadiene compounds (12-1) to (12-6) may be mixed simultaneously in a solvent, or the base and the amine compound are mixed in advance and then any of the substituted cyclopentadiene compounds (12-1) to (12-6) may be added to the mixture.
  • the reaction temperature is not particularly limited, and a temperature region that eliminates the need of low temperature equipment is industrially preferable and is, for example, in the range of 0 to 70° C., preferably in the range of 10 to 60° C.
  • This reaction efficiently produces a metal salt of any of the substituted cyclopentadiene compounds (12-1) to (12-6).
  • the metal salt of any of the substituted cyclopentadiene compounds (12-1) to (12-6) thus obtained may be used directly in the form of the reaction mixture or may be taken from the reaction mixture. The former case usually suffices.
  • the reaction for obtaining any of the substituted cyclopentadiene compounds (6-1) to (6-6) is usually performed in a solvent inert to the reaction.
  • a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene.
  • aromatic hydrocarbyl solvents such as benzene, toluene and xylene
  • solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually in the range of 1- to 200-fold by weight, preferably in the range of 3- to 30-fold by weight, with respect to any of the substituted cyclopentadiene compounds (12-1) to (12-6).
  • This reaction is usually performed, for example, by mixing the base, the amine compound and any of the substituted cyclopentadiene compounds (12-1) to (12-6) in a solvent and then adding any of the silicon halide compounds (13-1) to (13-6) to the mixture.
  • the substituted cyclopentadiene compounds (12-1) to (12-6) of interest can be produced.
  • the reaction temperature is not particularly limited, and a temperature region that eliminates the need of low temperature equipment is industrially advantageous and is, for example, in the range of 0 to 70° C., preferably in the range of 10 to 60° C.
  • the amount of the substituted cyclopentadienes (12-1) to (12-6) used is usually in the range of 0.5- to 5-fold by mol, preferably in the range of 0.8- to 3-fold by mol, with respect to the silicon halide compounds (13-1) to (13-6).
  • a water-insoluble organic solvent such as toluene, ethyl acetate or chlorobenzene may be added to the reaction mixture as needed, followed by separation into organic and aqueous layers.
  • the obtained organic layer is concentrated to obtain any of the substituted cyclopentadiene compounds (12-1) to (12-6).
  • the obtained substituted cyclopentadiene compound may be purified, if necessary, by a method such as distillation or column chromatography treatment.
  • 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 each 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; in the case that more than one E 1 groups exist, the E 1 groups may be the same or different from each other; in the case that more than one G groups exist, the G groups may be the same or different from each other; the E 2 groups may be the same or different from each other; and the E 3 groups may be the same or different from each other; and
  • 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 r (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 groups.
  • 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.
  • 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.
  • 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
  • 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 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 trimerization catalyst of the present invention is a trimerization catalyst comprising the transition metal complex (1) and is a catalyst capable of producing 1-hexene by ethylene trimerization.
  • the transition metal complex (1) can be brought into contact with an activating co-catalytic component to obtain a catalytic component for trimerization.
  • Examples of such an activating co-catalytic component can include the compounds (A) and (B) described above. Moreover, these compounds (A) and (B) may be used in combination.
  • a molar ratio between the compound (A) (in terms of the aluminum atom) and the transition metal complex (1) used as a catalytic component (compound (A) (in terms of the aluminum atom)/transition metal complex (1)) is usually 0.01 to 10000, preferably 5 to 5000. Also, a molar ratio between the compound (B) and the transition metal complex (1) used as a catalytic component (compound (B)/transition metal complex (1)) is usually 0.01 to 100, preferably 0.5 to 10.
  • the concentration of the transition metal complex (1) 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.
  • the method for contacting each catalytic component is not particularly limited.
  • the transition metal complex (1) may be brought into contact with the activating co-catalytic component to prepare a trimerization catalyst in advance, and then is supplied to a reactor.
  • these catalytic components may be supplied to a reactor in any order and subjected to contact treatment in the reactor.
  • the process for producing 1-hexene according to the present invention is a process for producing 1-hexene from ethylene and is a process for producing 1-hexene through the trimerization reaction of ethylene.
  • the trimerization reaction is not particularly limited and may be, for example, trimerization reaction using an aliphatic hydrocarbyl (e.g., butane, pentane, hexane, heptane and octane), an aromatic hydrocarbyl (e.g., benzene and toluene), or a hydrocarbyl halide (e.g., methylene dichloride and chlorobenzene) as a solvent, trimerization reaction in a slurry state, or trimerization reaction in ethylene in a gas state can be carried out.
  • an aliphatic hydrocarbyl e.g., butane, pentane, hexane, heptane and octane
  • aromatic hydrocarbyl e.g., benzene and toluene
  • a hydrocarbyl halide e.g., methylene dichloride and chlorobenzene
  • the trimerization reaction can be performed by any of batch, semi-continuous and continuous process.
  • the pressure of ethylene is usually in the range of normal pressure to 10 MPa, preferably in the range of normal pressure to 5 MPa.
  • the temperature of the trimerization reaction can usually be in the range of ⁇ 50° C. to 220° C. and is preferably in the range of 0° C. to 170° C., more preferably in the range of 50° C. to 120° C.
  • the time of the trimerization reaction can generally be determined appropriately according to the reaction apparatus of interest and can be in the range of 1 minute to 20 hours.
  • Examples of the catalytic component for olefin polymerization used in the present invention can include a solid catalytic component containing titanium, magnesium and a halogen as essential ingredients; and a catalytic component comprising a metallocene transition metal complex.
  • examples of the catalytic component for olefin polymerization can include a complex having a phenoxyimine ligand as reported in EP0874005.
  • solid catalytic component containing titanium, magnesium and a halogen as essential ingredients can include solid catalytic components described in, for example, JP 63-142008 A, JP 4-227604 A, JP 5-339319 A, JP 6-179720 A, JP 9-31119 A, JP 11-80234 A, JP 11-322833 A or the like.
  • Examples of the catalytic component for olefin polymerization comprising a transition metal complex containing metallocene can include a transition metal complex represented by the following general formula (2):
  • M 2 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • Cp 1 represents a group having a cyclopentadiene-type anionic skeleton
  • J 1 represents a group linking Cp 1 and D 1 by one or two atoms of Group 14 of the Periodic Table of the Elements
  • q represents 0 or 1; when q is 1, D 1 represents a group having a cyclopentadiene-type anionic skeleton or a group which links J 1 and M 2 and which is bonded to M 2 at its atom of Group 15 or 16 of the Periodic Table of the Elements, and when q is 0, D 1 represents a group having a cyclopentadiene-type anionic skeleton;
  • 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 atom
  • the catalytic component for olefin polymerization can include transition metal complexes represented by the following general formulas (3), (4) or (5):
  • M 3 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • Cp 2 and Cp 3 represent a group having a cyclopentadiene-type anionic skeleton
  • J 2 represents a group linking Cp 2 and Cp 3 by one or two atoms of Group 14 of the Periodic Table of the Elements
  • X 6 and X 7 each independently represent
  • M 4 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • Cp 4 represents a group having a cyclopentadiene-type anionic skeleton
  • J 3 represents a group linking Cp 4 and A 1 by one or two atoms of Group 14 of the Periodic Table of the Elements
  • a 1 represents a group which links J 3 and M 4 and which is bonded to M 4 at its atom of Group 15 or 16 of the Periodic Table of the Elements
  • X 8 and X 9 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
  • M 5 represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • a 2 represents an atom of Group 16 of the Periodic Table of the Elements
  • J 4 represents an atom of Group 14 of the Periodic Table of the Elements
  • Cp 5 represents a group having a cyclopentadiene-type anionic skeleton
  • X 10 , X 11 , R 14 , R 15 , R 16 and R 17 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
  • the transition metal complex represented by the general formula (2) 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 M 2 include titanium, zirconium and hafnium atoms, for example.
  • Examples of the group having a cyclopentadiene-type anionic skeleton, represented by Cp 1 or D 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 -neopent
  • ⁇ 5 -cyclopentadienyl, ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -fluorenyl and re-azulenyl groups, etc. are preferable.
  • J 1 is a group linking Cp 1 and D 1 by one or two atoms of Group 14 of the Periodic Table of the Elements.
  • J 1 is —SiR 2 —, —CR 2 —, —SiR 2 SiR 2 —, —CR 2 CR 2 —, —CR ⁇ CR—, —CR 2 SiR 2 — or —GeR 2 —.
  • R is a hydrogen atom, an alkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having up to 20 carbon atoms which may have a halogen atom as a substituent or a hydrocarbyl-substituted silyl group having up to 20 carbon atoms which may have a halogen atom as a substituent.
  • R groups may be the same or different.
  • R examples 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, (3,4-dimethylphenyl)methyl, (3,5-dimethylphen
  • the group which links J 1 and M 2 and which is bonded to M 2 at its atom of Group 15 or 16 of the Periodic Table of the Elements, represented by D 1 is, for example, —O—, —S—, —NR— or —PR—, preferably —NR—.
  • R is a hydrogen atom, an alkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having up to 20 carbon atoms which may have a halogen atom as a substituent or a hydrocarbyl-substituted silyl group having up to 20 carbon atoms which may have a halogen atom as a substituent.
  • R examples 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, (3,4-dimethylphenyl)methyl, (3,5-dimethylphen
  • examples of the group which links J 1 and M 2 and which is bonded to M 2 at its atom of Group 15 or 16 of the Periodic Table of the Elements, represented by D 1 include groups represented by the following general formulas (2-1), (2-2), (2-3) and (2-4):
  • R is a hydrogen atom, an alkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having up to 20 carbon atoms which may have a halogen atom as a substituent or a hydrocarbyl-substituted silyl group having up to 20 carbon atoms which may have a halogen atom as a substituent.
  • R examples 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, (3,4-dimethylphenyl)methyl, (3,5-dimethylphen
  • 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 12 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atom
  • Examples of the halogen atom in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) 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 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 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-butylpheny
  • 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 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) 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-te
  • any of these aralkyl groups may be substituted by a halogen atom.
  • halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • 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 hydrogen atoms in the aralkyl group by a halogen atom.
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) 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 hydrogen atoms in the alkoxy group by a halogen atom.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) 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
  • 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 hydrogen atoms in the aryloxy group by a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4) 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-trimethylphen
  • 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 hydrogen atoms in the aralkyloxy group by a halogen atom.
  • the R 12 groups are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 1.0 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-nony
  • the total number of the carbon atoms in these three R 12 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 of these groups by a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or hydrocarbyl halide groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups of these groups by a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or hydrocarbyl halide 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 hydrogen atoms in these groups by a halogen atom are more preferable.
  • the two R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 groups is 2 to 20, in X 4 , X 5 and the substituent on the benzene ring in the general formulas (2-1), (2-2), (2-3) and (2-4), the R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 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 13 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R 13 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 hydrogen atoms in these groups by a halogen atom. Of them, dimethylamino, diethylamino, di-
  • the transition metal complex represented by the general formula (2) is preferably a complex wherein q is 1, more preferably wherein q is 1, and D 1 is a group binding to M 2 by a nitrogen atom or a group represented by the general formula (2-1), even more preferably wherein q is 1, and D 1 is a group represented by the general formula (2-1).
  • transition metal complexes represented by the general formulas (3) and (4) 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 M 3 include titanium, zirconium and hafnium atoms. Zirconium and hafnium atoms are preferable.
  • 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 4 include titanium, zirconium and hafnium atoms. Titanium and zirconium atoms are preferable.
  • a 1 is a group linking J 3 and M 4 by an oxygen, sulfur, nitrogen or phosphorus atom
  • a 1 is, for example, —O—, —S—, —NR— or —PR—, preferably —NR—.
  • R is a hydrogen atom, an alkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having up to 20 carbon atoms which may have a halogen atom as a substituent or a hydrocarbyl-substituted silyl group having up to 20 carbon atoms which may have a halogen atom as a substituent.
  • R examples 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, (3,4-dimethylphenyl)methyl, (3,5-dimethylphen
  • J 2 is a group linking Cp 1 and Cp 3 by one or two atoms of Group 14 of the Periodic Table of the Elements
  • J 3 is a group linking Cp 4 and A 1 by one or two atoms of Group 14 of the Periodic Table of the Elements.
  • J 2 and J 3 are each independently —SiR 2 —, —CR 2 —, —SiR 2 SiR 2 —, —CR 2 CR 2 —, —CR ⁇ CR—, —CR 2 SiR 2 — or —GeR 2 —.
  • R is a hydrogen atom, an alkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having up to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having up to 20 carbon atoms which may have a halogen atom as a substituent or a hydrocarbyl-substituted silyl group having up to 20 carbon atoms which may have a halogen atom as a substituent.
  • a plurality of R moieties may be the same or different.
  • R examples 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, (3,4-dimethylphenyl)methyl, (3,5-dimethylphen
  • Examples of the group having a cyclopentadiene-type anionic skeleton represented by the substituents Cp 2 , Cp 3 and Cp 4 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 -cyclopentadienyl ⁇ 5 -methylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -tetramethylcyclopentadienyl, ⁇ 5 -indenyl, if-fluorenyl and ⁇ 5 -azulenyl groups, etc. are preferable.
  • halogen atoms in X 6 , X 7 , X 8 and X 9 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X 6 , X 7 , X 8 and X 9 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 6 , X 7 , X 8 and X 9 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,
  • 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 6 , X 7 , X 8 and X 9 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
  • any of these aralkyl groups may be substituted by a halogen atom.
  • halogen atom include fluorine, chlorine, bromine and iodine atoms.
  • 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 with a halogen atom.
  • Examples of the alkoxy group having 1 to 20 carbon atoms in X 6 , X 7 , X 8 and X 9 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 with a halogen atom.
  • Examples of the aryloxy group having 6 to 20 carbon atoms in X 6 , X 7 , X 8 and X 9 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-trimethylp henoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylp henoxy, 2,4,5-trimethylp henoxy, 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-butyl
  • 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 with a halogen atom.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms in X 6 , X 7 , X 8 and X 9 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,
  • 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 with a halogen atom.
  • the R 12 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, tort-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 12 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 of these groups by 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 of these groups by 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 hydrogen atoms in these groups by a halogen atom are more preferable.
  • the two R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 groups is 2 to 20, in X 6 , X 7 , X 8 and X 9 , the R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 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.
  • these two R 13 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R 13 groups are 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 hydrogen atoms in these groups by a halogen atom. Of them, dimethylamino, diethylamino, di-
  • the transition metal complex represented by the general formula (3) can be produced, for example, by a method described in JP 3290218B.
  • Examples of the complex represented by the general formula (3) include methylenebis(cyclopentadienyl)zirconium dichloride, isopropylidenebis(cyclopentadienyl)zirconium dichloride, diphenylmethylenebis(cyclopentadienyl)zirconium dichloride, 1,2-ethylene-bis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, diphenylsilylenebis(cyclopentadienyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(cyclopentadienyl)zirconium dichloride,
  • methylenebis(methylcyclopentadienyl)zirconium dichloride isopropylidenebis(methylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(methylcyclopentadienyl)zirconium dichloride, 1,2-ethylene-bis(methylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride, diphenylsilylenebis(methylcyclopentadienyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(methylcyclopentadienyl)zirconium dichloride,
  • methylenebis(n-butylcyclopentadienyl)zirconium dichloride isopropylidenebis(n-butylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(n-butylcyclopentadienyl)zirconium dichloride, 1,2-ethylene-bis(n-butylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(n-butylcyclopentadienyl)zirconium dichloride, diphenylsilylenebis(n-butylcyclopentadienyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(n-butylcyclopentadienyl)zirconium dichloride,
  • methylenebis(tert-butylcyclopentadienyl)zirconium dichloride isopropylidenebis(tert-butylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(tert-butylcyclopentadienyl)zirconium dichloride, 1,2-ethylene-bis(tert-butylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(tert-butylcyclopentadienyl)zirconium dichloride, diphenylsilylenebis(tert-butylcyclopentadienyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(tert-butylcyclopentadienyl)zirconium dichloride,
  • methylenebis(tetramethylcyclopentadienyl)zirconium dichloride isopropylidenebis(tetramethylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(tetramethylcyclopentadienyl)zirconium dichloride, 1,2-ethylene-bis(tetramethylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride, diphenylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride, 1,2-tetramethyldi silylene-bis(tetramethylcyclopentadienyl)zirconium dichloride,
  • methylenebis(indenyl)zirconium dichloride isopropylidenebis(indenyl)zirconium dichloride, diphenylmethylenebis(indenyl)zirconium dichloride, 1,2-ethylene-bis(indenyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, diphenylsilylenebis(indenyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(indenyl)zirconium dichloride,
  • methylenebis(fluorenyl)zirconium dichloride isopropylidenebis(fluorenyl)zirconium dichloride, diphenylmethylenebis(fluorenyl)zirconium dichloride, 1,2-ethylene-bis(fluorenyl)zirconium dichloride, dimethylsilylenebis(fluorenyl)zirconium dichloride, diphenylsilylenebis(fluorenyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(fluorenyl)zirconium dichloride,
  • methylenebis(azulenyl)zirconium dichloride isopropylidenebis(azulenyl)zirconium dichloride, diphenylmethylenebis(azulenyl)zirconium dichloride, 1,2-ethylene-bis(azulenyl)zirconium dichloride, dimethylsilylenebis(azulenyl)zirconium dichloride, diphenylsilylenebis(azulenyl)zirconium dichloride, 1,2-tetramethyldisilylene-bis(azulenyl)zirconium dichloride,
  • methylene(cyclopentadienyl)(indenyl)zirconium dichloride isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(indenyl)zirconium dichloride, 1,2-ethylene-(cyclopentadienyl)(indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride, 1,2-tetramethyldisilylene-(cyclopentadienyl)(indenyl)zirconium dichloride,
  • methylenebis(cyclopentadienyl)hafnium dichloride isopropylidenebis(cyclopentadienyl)hafnium dichloride, diphenylmethylenebis(cyclopentadienyl)hafnium dichloride, 1,2-ethylene-bis(cyclopentadienyl)hafnium dichloride, dimethylsilylenebis(cyclopentadienyl)hafnium dichloride, diphenylsilylenebis(cyclopentadienyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(cyclopentadienyl)hafnium dichloride,
  • methylenebis(methylcyclopentadienyl)hafnium dichloride isopropylidenebis(methylcyclopentadienyl)hafnium dichloride, diphenylmethylenebis(methylcyclopentadienyl)hafnium dichloride, 1,2-ethylene-bis(methylcyclopentadienyl)hafnium dichloride, dimethylsilylenebis(methylcyclopentadienyl)hafnium dichloride, diphenylsilylenebis(methylcyclopentadienyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(methylcyclopentadienyl)hafnium dichloride,
  • methylenebis(n-butylcyclopentadienyl)hafnium dichloride isopropylidenebis(n-butylcyclopentadienyl)hafnium dichloride, diphenylmethylenebis(n-butylcyclopentadienyl)hafnium dichloride, 1,2-ethylene-bis(n-butylcyclopentadienyl)hafnium dichloride, dimethylsilylenebis(n-butylcyclopentadienyl)hafnium dichloride, diphenylsilylenebis(n-butylcyclopentadienyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(n-butylcyclopentadienyl)hafnium dichloride,
  • methylenebis(tert-butylcyclopentadienyl)hafnium dichloride isopropylidenebis(tert-butylcyclopentadienyl)hafnium dichloride, diphenylmethylenebis(tert-butylcyclopentadienyl)hafnium dichloride, 1,2-ethylene-bis(tert-butylcyclopentadienyl)hafnium dichloride, dimethylsilylenebis(tert-butylcyclopentadienyl)hafnium dichloride, diphenylsilylenebis(tert-butylcyclopentadienyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(tert-butylcyclopentadienyl)hafnium dichloride,
  • methylenebis(tetramethylcyclopentadienyl)hafnium dichloride isopropylidenebis(tetramethylcyclopentadienyl)hafnium dichloride, diphenylmethylenebis(tetramethylcyclopentadienyl)hafnium dichloride, 1,2-ethylene-bis(tetramethylcyclopentadienyl)hafnium dichloride, dimethylsilylenebis(tetramethylcyclopentadienyl)hafnium dichloride, diphenylsilylenebis(tetramethylcyclopentadienyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(tetramethylcyclopentadienyl)hafnium dichloride,
  • methylenebis(indenyl)hafnium dichloride isopropylidenebis(indenyl)hafnium dichloride, diphenylmethylenebis(indenyl)hafnium dichloride, 1,2-ethylene-bis(indenyl)hafnium dichloride, dimethylsilylenebis(indenyl)hafnium dichloride, diphenylsilylenebis(indenyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(indenyl)hafnium dichloride,
  • methylenebis(fluorenyl)hafnium dichloride isopropylidenebis(fluorenyl)hafnium dichloride, diphenylmethylenebis(fluorenyl)hafnium dichloride, 1,2-ethylene-bis(fluorenyl)hafnium dichloride, dimethylsilylenebis(fluorenyl)hafnium dichloride, diphenylsilylenebis(fluorenyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(fluorenyl)hafnium dichloride,
  • methylenebis(azulenyl)hafnium dichloride isopropylidenebis(azulenyl)hafnium dichloride, diphenylmethylenebis(azulenyl)hafnium dichloride, 1,2-ethylene-bis(azulenyl)hafnium dichloride, dimethylsilylenebis(azulenyl)hafnium dichloride, diphenylsilylenebis(azulenyl)hafnium dichloride, 1,2-tetramethyldisilylene-bis(azulenyl)hafnium dichloride,
  • methylene(cyclopentadienyl)(indenyl)hafnium dichloride isopropylidene(cyclopentadienyl)(indenyl)hafnium dichloride, diphenylmethylene(cyclopentadienyl)(indenyl)hafnium dichloride, 1,2-ethylene-(cyclopentadienyl)(indenyl)hafnium dichloride, dimethylsilylene(cyclopentadienyl)(indenyl)hafnium dichloride, diphenylsilylene(cyclopentadienyl)(indenyl)hafnium dichloride, 1,2-tetramethyldisilylene-(cyclopentadienyl)(indenyl)hafnium dichloride,
  • the transition metal complex represented by the general formula (4) can be produced, for example, by a method described in JP 2535249B.
  • Examples of the complex represented by the general formula (4) include methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, methylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride, methylene(phenylamido)(cyclopentadienyl)titanium dichloride, methylene(benzylamido)(cyclopentadienyl)titanium dichloride, methylene(tert-butylphosphido)(cyclopentadienyl)titanium dichloride, methylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride, methylene(phenylphosphido)(cyclopentadienyl)titanium dichloride, methylene(benzylphosphido)(cyclopentadienyl)tit
  • diphenylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride diphenylsilylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(phenylamido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(benzylamido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(tert-butylphosphido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(phenylphosphido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(benzy
  • 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 5 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 2 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 4 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 5 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, tetramethylcyclopentadienyl, ⁇ 5 -indenyl and ⁇ 5 -fluorenyl groups, etc. are preferable.
  • halogen atoms in X 10 , X 11 , R 14 , R 15 , R 16 and R 17 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms in X 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 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 12 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-de
  • the total number of the carbon atoms in these three R 12 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 hydrocarbyl halide group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups of these groups by 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 of these groups by a halogen atom; and trisubstituted silyl groups having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsily
  • 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 two R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13 groups is 2 to 20, in X 10 , X 11 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 , the R 13 moieties each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in two R 13 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 13 groups may be bonded to each other to form a ring together with the nitrogen atom to which the two R 13 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 hydrogen atoms in these groups by a halogen atom. Of them, dimethylamino, diethylamino, di-
  • 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 18 and R 19 may be bonded to each other to form a ring together with J 4 to which R 18 and R 19 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 and anthracene rings. These rings may be substituted by a hydrocarbyl group having 1 to 20 carbon atoms or the like, or may contain a silicon atom. Examples of the ring containing a silicon atom include silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings.
  • the substituents X 10 and X 11 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 14 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 12 ) 3 , wherein the three R 12 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 R 12 groups is 1 to 20.
  • the transition metal complex represented by the general formula (5) can be produced, for example, by a method described in JP 9-87313 A.
  • Examples of the complex represented by the general formula (5) include: transition metal complexes represented by the general formula (5) wherein J 4 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 dich
  • transition metal complexes represented by the general formula (5) wherein J 4 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(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
  • An unbridged bismetallocene complex can also be used as the catalytic component for olefin polymerization, and examples thereof include bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(t-butylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride,
  • a transition metal complex of Group 4 of the Periodic Table of the Elements having an amide-pyridyl-aryl ligand can also be used as the catalytic component for olefin polymerization, and examples thereof include 2-(N-phenylamido-phenylmethyl)-6-(2- ⁇ -phenyl)-pyridyl hafnium dimethyl, 2-(N-phenylamido-phenylmethyl)-6-(2- ⁇ -1-naphthyl)-pyridyl hafnium dimethyl, 2[N-(2,6-diisopropylphenylamido)-phenylmethyl]-6-(2- ⁇ -phenyl)-pyridyl hafnium dimethyl, 2-[(N-phenylamido)-o-isopropylphenylmethyl]-6-(2- ⁇ -phenyl)-pyridyl hafnium dimethyl, 2[N-(2,6-diisopropylphenylamido
  • the olefin polymerization catalyst used in the present invention is a catalyst obtainable by bringing a catalytic component for olefin polymerization comprising the transition metal complex represented by the general formula (2), a catalytic component for trimerization comprising the transition metal complex represented by the general formula (1) and the activating co-catalytic component into contact with each other.
  • a 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.
  • a 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.
  • a 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.
  • a ratio between the mole of aluminum atoms in the compound (A) and the mole of titanium atoms in the solid catalytic component is usually 1 to 10000, preferably 1 to 2000, more preferably 2 to 600.
  • 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.
  • a catalytic component for olefin polymerization comprising the transition metal complex represented by the general formula (2) and the activating co-catalytic component may be supported on 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; or 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 the surface.
  • Modified inorganic oxides obtained by substituting active hydrogen in the surface hydroxy group by 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 trialkylchlorosilane such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilane such as triphenylchlorosilane, dialkyldichlorosilane such as dimethyldichlorosilane, diaryldichlorosilane such as diphenyldichlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, atyltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as triphenylmethoxysilane, dialkyldialkoxysilane such as dimethyldimethoxysilane, diaryldialkoxysilane such as diphenyldimethoxysilane,
  • magnesium compounds used as a carrier can include: magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride; aryloxy magnesium halide such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and carboxylate of magnesium such as magnesium laurate and magnesium stearate.
  • magnesium halide or 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 and halloysites.
  • smectite, montmorillonite, hectorite, Laponite or saponite is preferable, and 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 ⁇ 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 by 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 by 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 this monomer with additional monomer(s) having one or more polymerizable unsaturated groups.
  • a crosslinking polymerizable 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 amine, vinyl group-containing secondary amine, 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.
  • specific examples of the crosslinking polymerizable 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: olefin 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 olefin such as norbornene; alkenyl aromatic hydrocarbyl such as styrene; unsaturated carboxylic acid such as acrylic acid and methacrylic acid; unsaturated carboxylic ester 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 using aliphatic hydrocarbyl (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbyl (benzene, toluene, etc.) or hydrocarbyl halide (methylene dichloride, etc.) as a solvent, slurry polymerization, gas-phase polymerization performed in monomers in a gas state, or the like. Moreover, both continuous polymerization and batch polymerization may be used.
  • the present invention can produce a polymer having a butyl branch 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.
  • an ethylene molar fraction the total amount of ethylene and 1-hexene in the polymerization system is defined as 100 mol %
  • 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, for enhancing the economy.
  • 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 more increasing the number of butyl branches.
  • the polymerization pressure is preferably normal pressure to 5 MPa.
  • the polymerization time is generally determined appropriately according to the type of the polymer of interest and a reaction apparatus and can be in the range of 1 minute to 20 hours.
  • a chain transfer agent such as hydrogen can also be added for adjusting 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 more increasing the number of 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 enhancing 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.
  • the melting point of the ethylenic polymer is preferably lower than 130° C. from the viewpoint of enhancing 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 enhancing the processability of the polymer. Moreover, Mw/Mn is preferably 20 or lower for enhancing the mechanical strength of the polymer.
  • the molecular weight distribution (Mw/Mn) is a value (Mw/Mn) obtained by determining the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) by gel permeation chromatography against polystyrene standards and dividing Mw by Mn.
  • the ethylenic polymer is molded, for use, into various 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. Moreover, the moldings may be monolayer molding containing the ethylenic polymer or may be multilayer molding 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 package for semiconductor products or the like, cross-linked foamed moldings, injection foamed moldings, hollow moldings, blow bottles and squeeze bottles.
  • Apparatus EX270 manufactured by JEOL Ltd.
  • Sample cell Tube (5 mm in diameter)
  • Measurement solvent CDCl 3 or CD 2 Cl 2
  • Sample concentration 10 mg/0.5 mL (CDCl 3 or CD 2 Cl 2 )
  • Measurement temperature Room temperature (about 25° C.)
  • Measurement parameter Probe (5 mm in diameter)
  • EXMOD NON EXMOD NON
  • OBNUC 1 H accumulated number 16 times or more Repeat time: ACQTM 6 seconds
  • PD 1 second Internal standard CDCl 3 (7.26 ppm) or CD 2 Cl 2 (5.32 ppm)
  • Apparatus EX270 manufactured by JEOL Ltd.
  • Sample cell Tube (5 mm in diameter)
  • Measurement solvent CDCl 3 or CD 2 Cl 2
  • Sample concentration 30 mg/0.5 mL (CDCl 3 or CD 2 Cl 2 )
  • Measurement temperature Room temperature (about 25° C.)
  • Measurement parameter Probe (5 mm in diameter)
  • EXMOD BCM EXMOD BCM
  • OBNUC 13 C accumulated number 256 times or more Repeat time: ACQTM 1.79 seconds, PD 1.21 seconds
  • Internal standard CDCl 3 (77.0 ppm) or CD 2 Cl 2 (53.8 ppm)
  • EI-MS Electrode ionization mass spectrometry
  • complex 1 [1-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 2 [1-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 3 [1-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 4 [1-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 5 [1-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.80 g, 33.47 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (30 mL) were mixed. This mixture was heated to 50° C. and aniline (0.21 g, 2.23 mmol) was added and stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.00 g, 24.55 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.
  • complex 6 [1-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 7 [1-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.68 g, 28.45 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (30 mL) were mixed. This mixture was heated to 50° C. and aniline (0.18 g, 1.90 mmol) was added and stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (2.55 g, 20.87 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.
  • complex 8 [1-(3,5-di-n-hexylphenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 9 [1-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 10 [1-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.83 g, 34.48 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (85 mL) were mixed. This mixture was heated to 50° C. and aniline (0.21 g, 2.30 mmol) was added, and then, stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.09 g, 25.28 mmol) dissolved in tetrahydrofuran (21 mL) was added dropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.
  • complex 11 [1-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.49 g, 20.45 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were mixed. This mixture was heated to 50° C. and aniline (0.13 g, 1.36 mmol) was added and stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.83 g, 15.00 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise and stirred at 50° C. for 3.5 hours, and then was cooled to 0° C.
  • complex 12 [1-dimethyl(4-methoxyphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 13 [1-benzyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.51 g, 21.20 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (35 mL) were mixed. This mixture was heated to 50° C. and aniline (0.13 g, 1.41 mmol) was added and stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (1.90 g, 15.55 mmol) dissolved in tetrahydrofuran (9 mL) was added dropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.
  • complex 14 [9-dimethylphenylsilyl-octahydrofluorenyl]titanium trichloride
  • complex 15 [1-dimethylphenylsilyl-indenyl]titanium trichloride
  • complex 16 [1-dimethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 17 [1-dimethylphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride
  • tetrahydrofuran (30 mL) was added. This mixture was cooled to 0° C. and a 3% aqueous hydrochloric acid solution (9 mL) was added and stirred at room temperature for 2 hours. Toluene and water were added to separate an organic phase, and the organic phase was washed with a saturated aqueous sodium chloride solution. The organic phase was dried over magnesium sulfate, and then filtrated. The solvent was removed under reduced pressure. To the resultant mixture, hexane (60 mL) was added.
  • complex 18 [1-dimethyl(1-naphthyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 19 [1-(3,5-bis(trifluoromethyl)phenyl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 20 [3-methyl-1-dimethylphenylsilylcyclopentadienyl]titanium trichloride
  • complex 21 [1-dimethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride
  • complex 22 [1-(9-anthryl)dimethylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 23 [1-(cyclotetramethylene)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 24 [1-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • sodium hydride (0.98 g, 40.95 mmol in terms of pure sodium hydride) dispersed in mineral oil and tetrahydrofuran (57 mL) were mixed. This mixture was heated to 50° C. and aniline (0.25 g, 2.73 mmol) was added and stirred at 50° C. for one hour. To this, a solution of 1,2,3,4-tetramethylcyclopenta-1,3-diene (3.67 g, 30.03 mmol) dissolved in tetrahydrofuran (14 mL) was added dropwise and stirred at 50° C. for 2 hours, and then was cooled to 0° C.
  • complex 25 [1-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride
  • complex 26 [3-tert-butyl-1-dimethylphenylsilylcyclopentadienyl]titanium trichloride

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US13/498,980 2009-09-30 2010-09-30 Transition metal complex, preparation method for said transition metal complex, trimerization catalyst, preparation method for 1-hexene, preparation method for ethylene polymer, substituted cyclopentadiene compound, and preparation method for said substituted cyclopentadiene compound Abandoned US20120184431A1 (en)

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US20140018565A1 (en) * 2011-03-29 2014-01-16 Sumitomo Chemical Company, Limited Method for producing transition metal complex, catalyst for trimerization, method for producing 1-hexene, method for producing substituted cyclopentadiene compound (2)
US8937195B2 (en) 2011-03-29 2015-01-20 Sumitomo Chemical Company, Limited Method for producing the transition metal complex, catalyst for trimerization, method for producing 1-hexene, method for producing the substituted cyclopentadiene compound (1)
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